O-cyclopropylcyclohexyl-carboxanilides and their use as fungicides

ABSTRACT

The present invention relates to O-CYCLOPROPYLCYCLOHEXYL-CARBOXANILIDES derivatives of formula (I); their process of preparation, their use as fungicide, particularly in the form of fungicide compositions, and methods for the control of phytopathogenic fungi, notably of plants, using these compounds or compositions.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a §371 National Stage Application ofPCT/EP2011/059055 filed Jun. 1, 2011, which claims priority to EuropeanApplication No. 10356020.7 filed Jun. 3, 2010, European Application No.10191262.4 filed Nov. 15, 2010, European Application No. 10356032.2filed Nov. 15, 2010 and U.S. Provisional Application No. 61/368,003,filed Jul. 27, 2010.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel ortho-substitutedcyclopropylcyclohexyl carboxamide which have microbiocidal activity, inparticular fungicidal activity. The invention also relates to thepreparation of these compounds, to novel intermediates used in thepreparation of these compounds, to agrochemical compositions whichcomprise at least one of the novel compounds as active ingredient, tothe preparation of the compositions mentioned and to the use of theactive ingredients or compositions in agriculture or horticulture forcontrolling or preventing infestation of plants by phytopathogenicmicroorganisms, preferably fungi.

2. Description of Related Art

WO-A 2003/074491 discloses certainortho-unsubstituted-cyclopropyl-phenyl-carboxamides:

SUMMARY

The present invention provides ortho-substituted cyclopropylcyclohexylcarboxamide compounds of formula (I) which are new:

in which

-   R¹ represents hydrogen, fluoro, chloro or bromo;-   R² represents hydrogen fluoro, chloro or bromo;-   R³ represents optionally substituted C₂₋₁₂ alkyl, optionally    substituted C₂₋₁₂ alkenyl, optionally substituted C₂₋₁₂ alkynyl,    optionally substituted C₃₋₁₂ cycloalkyl, optionally substituted    phenyl or optionally substituted heterocyclyl;-   A represents one of the radicals A1 to A18 below

-   R¹⁸ represents hydrogen, cyano, halogen, nitro, C₁-C₄-alkyl,    C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, C₁-C₄-haloalkyl,    C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in each case 1 to 5    halogen atoms, aminocarbonyl or aminocarbonyl-C₁-C₄-alkyl,-   R¹⁹ represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy    or C₁-C₄-alkylthio,-   R²⁰ represents hydrogen, C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl,    C₂-C₆-alkenyl, C₃-C₆-cycloalkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl,    C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkyl,    C₁-C₄-haloalkylthio-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl having    in each case 1 to 5 halogen atoms, or phenyl,-   R²¹ and R²² independently of one another represent hydrogen,    halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms,-   R²³ represents halogen, cyano or C₁-C₄-alkyl, or C₁-C₄-haloalkyl or    C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms,-   R²⁴ and R²⁵ independently of one another represent hydrogen,    halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms,-   R²⁶ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl    having 1 to 5 halogen atoms,-   R²⁷ represents hydrogen, halogen, hydroxyl, cyano, C₁-C₆-alkyl,    C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in    each case 1 to 5 halogen atoms,-   R²⁸ represents halogen, hydroxyl, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy,    C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio or    C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms,-   R²⁹ represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy,    C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy having in each    case 1 to 5 halogen atoms, C₁-C₄-alkylsulphinyl or    C₁-C₄-alkylsulphonyl,-   R³⁰ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen    atoms,-   R³¹ represents C₁-C₄-alkyl,-   Q¹ represents S (sulphur), SO, SO₂ or CH₂,-   p represents 0, 1 or 2, where R³¹ represents identical or different    radicals if p represents 2,-   R³² represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen    atoms,-   R³³ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen    atoms,-   R³⁴ and R³⁵ independently of one another represent hydrogen,    halogen, amino, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen    atoms,-   R³⁶ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl    having 1 to 5 halogen atoms,-   R³⁷ and R³⁸ independently of one another represent hydrogen,    halogen, amino, nitro, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5    halogen atoms,-   R³⁹ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl    having 1 to 5 halogen atoms,-   R⁴⁰ represents hydrogen, halogen, amino, C₁-C₄-alkylamino,    di-(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having    1 to 5 halogen atoms,-   R⁴¹ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5    halogen atoms,-   R⁴² represents hydrogen, halogen, amino, C₁-C₄-alkylamino,    di-(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having    1 to 5 halogen atoms,-   R⁴³ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5    halogen atoms,-   R⁴⁴ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5    halogen atoms,-   R⁴⁵ represents hydrogen or C₁-C₄-alkyl,-   R⁴⁶ represents halogen or C₁-C₄-alkyl,-   R⁴⁷ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen    atoms,-   R⁴⁸ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl    having 1 to 5 halogen atoms,-   R⁴⁹ represents halogen, hydroxyl, C₁-C₄-alkyl, C₁-C₄-alkoxy,    C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio or    C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms,-   R⁵⁰ represents C₁-C₄-alkyl;

Each alkyl moiety is a straight or branched chain and is, for example,methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl,n-butyl, sec-butyl, iso-butyl, tert-butyl or neo-pentyl.

When present, each optional substituent on an alkyl moiety is,independently, selected from halo, hydroxy, cyano, C₁₋₄ alkoxy C(═O),formyl, nitro, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio, C₁₋₄haloalkylthio.

Alkenyl and alkynyl moieties can be in the form of straight or branchedchains. The alkenyl moieties, where appropriate, can be of either the(E)- or (Z)-configuration. Examples are vinyl, allyl and propargyl.

When present, each optional substituent on alkenyl or on alkynyl is,independently, selected from those optional substituents given above foran alkyl moiety.

Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

When present, each optional substituent on cycloalkyl is, independently,selected from C₁₋₃ alkyl and those optional substituents given above foran alkyl moiety.

The term heterocyclyl refers to a non-aromatic or aromatic ringcontaining up to 10 atoms including one or more (preferably one or two)heteroatoms selected, each independently, from O, S and N. Examples ofsuch rings include 1,3-dioxolanyl, tetrahydrofuranyl, morpholinyl,thienyl and furyl.

When present, each optional substituent on phenyl or on heterocyclyl is,independently, selected from C₁₋₆ alkyl and those optional substituentsgiven above for an alkyl moiety. When present, there are up to fouroptional substituents on phenyl, each independently selected.

When present, each optional substituent on an alkyl moiety is,independently, selected from the preferred list of halo, hydroxy,methoxy, trifluoromethoxy, difluoromethoxy, cyano and nitro.

When present, each optional substituent on alkenyl or on alkynyl is,independently, selected from the preferred list of halo and cyano.

When present, each optional substituent on cycloalkyl is, independently,selected from the preferred list of methyl, ethyl, trifluoromethyl,methoxy, trifluoromethoxy and cyano.

When present, each optional substituent on phenyl or on a heterocyclylgroup is, independently, selected from the preferred list of halo,hydroxy, methoxy, trifluoromethoxy, difluoromethoxy and cyano.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

-   R¹ and R² preferably are, independently, hydrogen or fluoro.-   R¹ and R² particularly preferably are hydrogen.-   R³ preferably is C₂₋₆ alkyl, optionally substituted C₃₋₈ cycloalkyl,    phenyl, thienyl or furyl.-   R³ particularly preferably is C₂₋₆ alkyl, optionally substituted    C₃₋₈ cycloalkyl.-   R³ very particularly preferably is C₂₋₆ alkyl, optionally    substituted cyclopropyl.-   A particularly preferably represents one of the radicals A1, A2, A3,    A4, A5, A6, A9, A10, A11, A12 or A17.-   A particularly preferably represents one of the radicals    -   A1, A2, A4, A5, A6, A9, A11, A12, A16, A17.-   A very particularly preferably represents one of the radicals    -   A1, A2, A4, A5, A11, A12, A16, A17.-   A very particularly preferably represents the radical A1.-   A furthermore very particularly preferably represents the radical    A2.-   A furthermore very particularly preferably represents the radical    A4.-   A furthermore very particularly preferably represents the radical    A5.-   A furthermore very particularly preferably represents the radical    A6.-   A furthermore very particularly preferably represents the radical    A9.-   A furthermore very particularly preferably represents the radical    A11.-   A furthermore very particularly preferably represents the radical    A12.-   A furthermore very particularly preferably represents the radical    A16.-   A furthermore very particularly preferably represents the radical    A17.-   R¹⁸ preferably represents hydrogen, cyano, fluorine, chlorine,    bromine, iodine, methyl, ethyl, isopropyl, methoxy, ethoxy,    methylthio, ethylthio, cyclopropyl, C₁-C₂-haloalkyl,    C₁-C₂-haloalkoxy having in each case 1 to 5 fluorine, chlorine    and/or bromine atoms, trifluoromethylthio, difluoromethylthio,    aminocarbonyl, aminocarbonylmethyl or aminocarbonylethyl.-   R¹⁸ particularly preferably represents hydrogen, fluorine, chlorine,    bromine, iodine, methyl, ethyl, isopropyl, monofluoromethyl,    monofluoroethyl, difluoromethyl, trifluoromethyl,    difluorochloromethyl, trichloromethyl, dichloromethyl, cyclopropyl,    methoxy, ethoxy, trifluoromethoxy, trichloromethoxy, methylthio,    ethylthio, trifluoromethylthio or difluoromethylthio.-   R¹⁸ very particularly preferably represents hydrogen, fluorine,    chlorine, bromine, iodine, methyl, isopropyl, monofluoromethyl,    monofluoroethyl, difluoromethyl, trifluoromethyl,    difluorochloromethyl, dichloromethyl or trichloromethyl.-   R¹⁸ especially preferably represents methyl, difluoromethyl,    trifluoromethyl, dichloromethyl or 1-fluoroethyl.-   R¹⁸ especially very preferably represents difluoromethyl or    dichloromethyl.-   R¹⁹ preferably represents hydrogen, fluorine, chlorine, bromine,    iodine, methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio.-   R¹⁹ particularly preferably represents hydrogen, fluorine, chlorine,    bromine, iodine or methyl.-   R¹⁹ very particularly preferably represents hydrogen, fluorine,    chlorine or methyl.-   R¹⁹ especially preferably represents fluorine, chlorine.-   R²⁰ preferably represents hydrogen, methyl, ethyl, n-propyl,    isopropyl, C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or    bromine atoms, hydroxymethyl, hydroxyethyl, cyclopropyl,    cyclopentyl, cyclohexyl or phenyl.-   R²⁰ particularly preferably represents hydrogen, methyl, ethyl,    isopropyl, trifluoromethyl, difluoromethyl, hydroxymethyl,    hydroxyethyl or phenyl.-   R²⁰ very particularly preferably represents hydrogen, methyl,    trifluoromethyl or phenyl.-   R²⁰ especially preferably represents methyl.

Particularly preferred are compounds according to formula (I) whereinR¹⁸ is difluoromethyl or dichloromethyl, R¹⁹ is fluorine or chlorine,and R²⁰ is methyl.

Particularly preferred are compounds according to formula (I) whereinR¹⁸ is difluoromethyl, R¹⁹ is fluorine, and R²⁰ is methyl.

-   R²¹ and R²² independently of one another preferably represent    hydrogen, fluorine, chlorine, bromine, methyl, ethyl or    C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine    atoms.-   R²¹ and R²² independently of one another particularly preferably    represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl,    difluoromethyl, trifluoromethyl, difluorochloromethyl or    trichloromethyl.-   R²¹ and R²² independently of one another very particularly    preferably represent hydrogen, fluorine, chlorine, bromine, methyl,    ethyl, difluoromethyl, trifluoromethyl or trichloromethyl.-   R²¹ and R²² especially preferably each represent hydrogen.-   R²³ preferably represents fluorine, chlorine, bromine, cyano,    methyl, ethyl, C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy having in each    case 1 to 5 fluorine, chlorine and/or bromine atoms.-   R²³ particularly preferably represents fluorine, chlorine, bromine,    cyano, methyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy,    difluorochloromethoxy or trichloromethoxy.-   R²³ very particularly preferably represents fluorine, chlorine,    bromine, iodine, methyl, trifluoromethyl or trifluoromethoxy.-   R²³ especially preferably represents methyl or trifluoromethyl.-   R²⁴ and R²⁵ independently of one another preferably represent    hydrogen, fluorine, chlorine, bromine, methyl, ethyl or    C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine    atoms.-   R²⁴ and R²⁵ independently of one another particularly preferably    represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl,    difluoromethyl, trifluoromethyl, difluorochloromethyl or    trichloromethyl.-   R²⁴ and R²⁵ independently of one another very particularly    preferably represent hydrogen, fluorine, chlorine, bromine, methyl,    ethyl, difluoromethyl, trifluoromethyl or trichloromethyl.-   R²⁴ and R²⁵ especially preferably each represent hydrogen.-   R²⁶ preferably represents hydrogen, fluorine, chlorine, bromine,    iodine, methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine,    chlorine and/or bromine atoms.-   R²⁶ particularly preferably represents hydrogen, fluorine, chlorine,    bromine, iodine, methyl or trifluoromethyl.-   R²⁶ very particularly preferably represents fluorine, chlorine,    bromine, iodine, methyl or trifluoromethyl.-   R²⁷ preferably represents hydrogen, fluorine, chlorine, bromine,    iodine, hydroxyl, cyano, C₁-C₄-alkyl, C₁-C₂-haloalkyl,    C₁-C₂-haloalkoxy or C₁-C₂-haloalkylthio having in each case 1 to 5    fluorine, chlorine and/or bromine atoms.-   R²⁷ particularly preferably represents hydrogen, fluorine, chlorine,    bromine, iodine, hydroxyl, cyano, methyl, ethyl, n-propyl,    isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, difluoromethyl,    trifluoromethyl, difluorochloromethyl, trichloromethyl,    trifluoromethoxy, difluoromethoxy, difluorochloromethoxy,    trichloromethoxy, trifluoromethylthio, difluoromethylthio,    difluorochloromethylthio or trichloromethylthio.-   R²⁷ very particularly preferably represents hydrogen, fluorine,    chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl    or trichloromethyl.-   R²⁷ especially preferably represents iodine, methyl, difluoromethyl    or trifluoromethyl.-   R²⁸ preferably represents fluorine, chlorine, bromine, iodine,    hydroxyl, cyano, C₁-C₄-alkyl, methoxy, ethoxy, methylthio,    ethylthio, difluoromethylthio, trifluoromethylthio, C₁-C₂-haloalkyl    or C₁-C₂-haloalkoxy having in each case 1 to 5 fluorine, chlorine    and/or bromine atoms.-   R²⁸ particularly preferably represents fluorine, chlorine, bromine,    iodine, hydroxyl, cyano, methyl, ethyl, n-propyl, isopropyl,    n-butyl, isobutyl, sec-butyl, tert-butyl, trifluoromethyl,    difluoromethyl, difluorochloromethyl, trichloromethyl, methoxy,    ethoxy, methylthio, ethylthio, difluoromethylthio,    trifluoromethylthio, trifluoromethoxy, difluoromethoxy,    difluorochloromethoxy or trichloromethoxy.-   R²⁸ very particularly preferably represents fluorine, chlorine,    bromine, iodine, methyl, trifluoromethyl, difluoromethyl or    trichloromethyl.-   R²⁹ preferably represents hydrogen, fluorine, chlorine, bromine,    iodine, cyano, C₁-C₄-alkyl, methoxy, ethoxy, methylthio, ethylthio,    C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy having in each case 1 to 5    fluorine, chlorine and/or bromine atoms, C₁-C₂-alkylsulphinyl or    C₁-C₂-alkylsulphonyl.-   R²⁹ particularly preferably represents hydrogen, fluorine, chlorine,    bromine, iodine, cyano, n-propyl, isopropyl, n-butyl, isobutyl,    sec-butyl, tert-butyl, trifluoromethyl, difluoromethyl,    difluorochloromethyl, trichloromethyl, methoxy, ethoxy, methylthio,    ethylthio, trifluoromethoxy, difluoromethoxy, difluorochloromethoxy,    trichloromethoxy, methylsulphinyl or methylsulphonyl.-   R²⁹ very particularly preferably represents hydrogen, fluorine,    chlorine, bromine, iodine, n-propyl, isopropyl, n-butyl, isobutyl,    sec-butyl, tert-butyl, trifluoromethyl, difluoromethyl,    trichloromethyl, methylsulphinyl or methylsulphonyl.-   R²⁹ especially preferably represents hydrogen.-   R³⁰ preferably represents methyl, ethyl or C₁-C₂-haloalkyl having 1    to 5 fluorine, chlorine and/or bromine atoms.-   R³⁰ particularly preferably represents methyl, ethyl,    trifluoromethyl, difluoromethyl, difluorochloromethyl or    trichloromethyl.-   R³¹ preferably represents methyl or ethyl.-   R³¹ particularly preferably represents methyl.-   Q¹ preferably represents S (sulphur), SO or CH₂,-   p preferably represents 0 or 1,-   R³² preferably represents methyl, ethyl or C₁-C₂-haloalkyl having 1    to 5 fluorine, chlorine and/or bromine atoms.-   R³² particularly preferably represents methyl, ethyl,    trifluoromethyl, difluoromethyl, difluorochloromethyl or    trichloromethyl.-   R³² very particularly preferably represents methyl, trifluoromethyl,    difluoromethyl or trichloromethyl.-   R³³ preferably represents methyl, ethyl or C₁-C₂-haloalkyl having 1    to 5 fluorine, chlorine and/or bromine atoms.-   R³³ particularly preferably represents methyl, ethyl,    trifluoromethyl, difluoromethyl, difluorochloromethyl or    trichloromethyl.-   R³³ very particularly preferably represents methyl, trifluoromethyl,    difluoromethyl or trichloromethyl.-   R³⁴ and R³⁵ independently of one another preferably represent    hydrogen, fluorine, chlorine, bromine, amino, methyl, ethyl or    C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine    atoms.-   R³⁴ and R³⁵ independently of one another particularly preferably    represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl,    trifluoromethyl, difluoromethyl, difluorochloromethyl or    trichloromethyl.-   R³⁴ and R³⁵ independently of one another very particularly    preferably represent hydrogen, fluorine, chlorine, bromine, methyl,    trifluoromethyl, difluoromethyl or trichloromethyl.-   R³⁴ and R³⁵ especially preferably each represent hydrogen.-   R³⁶ preferably represents hydrogen, fluorine, chlorine, bromine,    iodine, methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine,    chlorine and/or bromine atoms.-   R³⁶ particularly preferably represents hydrogen, fluorine, chlorine,    bromine, iodine, methyl, ethyl, trifluoromethyl, difluoromethyl,    difluorochloromethyl or trichloromethyl.-   R³⁶ very particularly preferably represents hydrogen, fluorine,    chlorine, bromine, iodine, methyl, trifluoromethyl, difluoromethyl    or trichloromethyl.-   R³⁶ especially preferably represents methyl.-   R³⁷ and R³⁸ independently of one another preferably represent    hydrogen, fluorine, chlorine, bromine, amino, nitro, methyl, ethyl    or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine    atoms.-   R³⁷ and R³⁸ independently of one another particularly preferably    represent hydrogen, fluorine, chlorine, bromine, nitro, methyl,    ethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl or    trichloromethyl.-   R³⁷ and R³⁸ independently of one another very particularly    preferably represent hydrogen, fluorine, chlorine, bromine, methyl,    trifluoromethyl, difluoromethyl or trichloromethyl.-   R³⁷ and R³⁸ especially preferably each represent hydrogen.-   R³⁹ preferably represents hydrogen, fluorine, chlorine, bromine,    methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine    and/or bromine atoms,-   R³⁹ particularly preferably represents hydrogen, fluorine, chlorine,    bromine, methyl, ethyl, trifluoromethyl, difluoromethyl,    difluorochloromethyl or trichloromethyl.-   R³⁹ very particularly represents hydrogen, fluorine, chlorine,    bromine, methyl, trifluoromethyl, difluoromethyl or trichloromethyl.-   R³⁹ especially preferably represents methyl.-   R⁴⁰ preferably represents hydrogen, fluorine, chlorine, bromine,    amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, methyl, ethyl    or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine    atoms.-   R⁴⁰ particularly preferably represents hydrogen, fluorine, chlorine,    bromine, amino, methylamino, dimethylamino, cyano, methyl, ethyl,    trifluoromethyl, difluoromethyl, difluorochloromethyl or    trichloromethyl.-   R⁴⁰ very particularly preferably represents hydrogen, fluorine,    chlorine, bromine, amino, methylamino, dimethylamino, methyl,    trifluoromethyl, difluoromethyl or trichloromethyl.-   R⁴⁰ especially preferably represents amino, methylamino,    dimethylamino, methyl or trifluoromethyl.-   R⁴¹ preferably represents fluorine, chlorine, bromine, methyl, ethyl    or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine    atoms.-   R⁴¹ particularly preferably represents fluorine, chlorine, bromine,    methyl, ethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl    or trichloromethyl.-   R⁴¹ very particularly preferably represents fluorine, chlorine,    bromine, methyl, trifluoromethyl, difluoromethyl or trichloromethyl.-   R⁴¹ especially preferably represents methyl, trifluoromethyl or    difluoromethyl.-   R⁴² preferably represents hydrogen, fluorine, chlorine, bromine,    amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, methyl, ethyl    or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine    atoms.-   R⁴² particularly preferably represents hydrogen, fluorine, chlorine,    bromine, amino, methylamino, dimethylamino, cyano, methyl, ethyl,    trifluoromethyl, difluoromethyl, difluorochloromethyl or    trichloromethyl.-   R⁴² very particularly preferably represents hydrogen, fluorine,    chlorine, bromine, amino, methylamino, dimethylamino, methyl,    trifluoromethyl, difluoromethyl or trichloromethyl.-   R⁴² especially preferably represents amino, methylamino,    dimethylamino, methyl or trifluoromethyl.-   R⁴³ preferably represents fluorine, chlorine, bromine, methyl, ethyl    or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine    atoms.-   R⁴³ particularly preferably represents fluorine, chlorine, bromine,    methyl, ethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl    or trichloromethyl.-   R⁴³ very particularly preferably represents fluorine, chlorine,    bromine, methyl, trifluoromethyl, difluoromethyl or trichloromethyl.-   R⁴³ especially preferably represents methyl, trifluoromethyl or    difluoromethyl.-   R⁴⁴ preferably represents fluorine, chlorine, bromine, methyl, ethyl    or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine    atoms.-   R⁴⁴ particularly preferably represents fluorine, chlorine, bromine,    methyl, ethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl    or trichloromethyl.-   R⁴⁴ very particularly preferably represents fluorine, chlorine,    bromine, methyl, trifluoromethyl, difluoromethyl or trichloromethyl.-   R⁴⁵ preferably represents hydrogen, methyl or ethyl.-   R⁴⁵ particularly preferably represents methyl.-   R⁴⁶ preferably represents fluorine, chlorine, bromine, methyl or    ethyl.-   R⁴⁶ particularly preferably represents fluorine, chlorine or methyl.-   R⁴⁷ preferably represents methyl, ethyl or C₁-C₂-haloalkyl having 1    to 5 fluorine, chlorine and/or bromine atoms.-   R⁴⁷ particularly preferably represents methyl, ethyl,    trifluoromethyl, difluoromethyl, difluorochloromethyl or    trichloromethyl.-   R⁴⁷ very particularly preferably represents methyl, trifluoromethyl,    difluoromethyl or trichloromethyl.-   R⁴⁷ especially preferably represents methyl or trifluoromethyl.-   R⁴⁸ preferably represents hydrogen, fluorine, chlorine, bromine,    methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine    and/or bromine atoms.-   R⁴⁸ particularly preferably represents hydrogen, fluorine, chlorine,    bromine, methyl or trifluoromethyl.-   R⁴⁹ preferably represents fluorine, chlorine, bromine, iodine,    hydroxyl, C₁-C₄-alkyl, methoxy, ethoxy, methylthio, ethylthio,    difluoromethylthio, trifluoromethylthio, C₁-C₂-haloalkyl or    C₁-C₂-haloalkoxy having in each case 1 to 5 fluorine, chlorine    and/or bromine atoms.-   R⁴⁹ particularly preferably represents fluorine, chlorine, bromine,    iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,    sec-butyl, tert-butyl, trifluoromethyl, difluoromethyl,    difluorochloromethyl or trichloromethyl.-   R⁴⁹ very particularly preferably represents fluorine, chlorine,    bromine, iodine, methyl, trifluoromethyl, difluoromethyl or    trichloromethyl.-   R⁵⁰ preferably represents methyl, ethyl, n-propyl or isopropyl.-   R⁵⁰ particularly preferably represents methyl or ethyl.

Preference is given to those compounds of the formula (I) in which allradicals each have the preferred meanings mentioned above.

Particular preference is given to those compounds of the formula (I) inwhich all radicals each have the particularly preferred meaningsmentioned above.

Compounds of formula (II):

where R¹, R² and R³ are defined above for a compound of formula (I), arealso novel and are useful as intermediates in the preparation ofcompounds of formula (I).

The compounds of formula (I) may exist as different geometric or opticalisomers or in different tautomeric forms. This invention covers all suchisomers and tautomers and mixtures thereof in all proportions as well asisotopic forms such as deuterated compounds.

The compounds according to formula (I) may be prepared according to thefollowing reaction scheme P0.

The compounds according to formula (I) may be prepared according to thereaction scheme P0 wherein in step 1 a compound according to formula(III)

wherein R¹, R² and R³ is as defined above;are reacted in the presence of a catalyst at elevated temperature andpressure to obtain the compounds according to formula (II)

wherein R¹, R² and R³ is as defined above;wherein in step 2 the compounds according to formula (II) as defined instep 1are reacted with compounds according to formula (IV)

with X being halogen or hydroxy;to obtain the compounds according to formula (I)

wherein A, R¹, R² and R³ is as defined above;

Most materials, in particular heterocyclic acids and acid halides [thatis, compounds of formula (IV)] are generally known from the literature,are commercially available or may be synthesized according to knownmethods (e.g. see WO-A 03/074491).

The compounds according to formula (III) are known from prior art asdescribed in WO-A 2003/074491.

The compounds of formula (II) [where R¹ to R³ is as defined above for acompound according to formula (I)] is obtained from a compound offormula (III) by catalytical reduction, e.g Ru/C optionally in a solvent(such as methanol, ethanol or THF) at elevated temperature and pressure,to produce a crude isomere mixture of a compound of formula (II), whichmay be further purified by standard techniques.

A cis-/trans-mixture of a compound according to formula (II) may beextracted and subsequent separation of the cis- and trans-isomersachieved by using flash chromatography.

The reduction of step 1 is usually carried out at elevated temperaturesof 0 to 200° C., preferably 0 to 120° C., more preferably of 50 to 120°C., and can be carried out at standard pressure or under excess pressurewhich means pressure up to 150 bar, preferably 1 to 150 bar, morepreferably 5 to 120 bar, more preferably 10 to 100 bar. Additionalranges are 10 to 180° C., 20 to 150° C. and 50 to 150° C.

The reduction according to step 1 with the chlorinating agent is carriedout neat or in the presence of a solvent which is inert under theprevailing reaction conditions. Use may be made, as diluents, forexample, of mono or polychlorinated aliphatic or aromatic hydrocarbonsor mixtures thereof. Examples of suitable diluents are chlorobenzene,dichlorobenzenes, trichlorobenzenes, chlorotoluenes,chlorobenzotrifluorides, methylene chloride, dichloroethane, chloroformor carbon tetrachloride. Preferred diluents are chlorobenzene,1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene,1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene,4-chloro-trifluoromethylbenzene, 1,3,5-trichlorobenzene, 2chlorotoluene, 3-chlorotoluene, 4-chlorotoluene or a mixture thereof.Use is particularly preferably made of chlorobenzene.

The reduction according to step 1 is carried out neat or in the presenceof a suitable catalyst such a catalyst is Ru/C.

Surprisingly, it has now been found that the novel compounds of formula(I) have, for practical purposes, a very advantageous spectrum ofactivities for protecting plants against diseases that are caused byfungi as well as by bacteria and viruses.

The compounds of formula (I) can be used in the agricultural sector andrelated fields of use as active ingredients for controlling plant pests.The novel compounds are distinguished by excellent activity at low ratesof application, by being well tolerated by plants and by beingenvironmentally safe. They have very useful curative, preventive andsystemic properties and are used for protecting numerous cultivatedplants. The compounds of formula I can be used to inhibit or destroy thepests that occur on plants or parts of plants (fruit, blossoms, leaves,stems, tubers, roots) of different crops of useful plants, while at thesame time protecting also those parts of the plants that grow later e.g.from phytopathogenic microorganisms.

It is also possible to use compounds of formula (I) as dressing agentsfor the treatment of plant propagation material, in particular of seeds(fruit, tubers, grains) and plant cuttings (e.g. rice), for theprotection against fungal infections as well as against phytopathogenicfungi occurring in the soil.

Furthermore the compounds according to present invention may be used forcontrolling fungi in related areas, for example in the protection oftechnical materials, including wood and wood related technical products,in food storage, in hygiene management, etc.

The compounds of formula (I) are, for example, effective against thephytopathogenic fungi of the following classes:

Some pathogens of fungal diseases which can be treated according to theinvention may be mentioned by way of example, but not by way oflimitation:

Powdery Mildew Diseases such as Blumeria diseases caused for example byBlumeria graminis; Podosphaera diseases caused for example byPodosphaera leucotricha; Sphaerotheca diseases caused for example bySphaerotheca fuliginea; Uncinula diseases caused for example by Uncinulanecator;Rust Diseases such as Gymnosporangium diseases caused for example byGymnosporangium sabinae; Hemileia diseases caused for example byHemileia vastatrix; Phakopsora diseases caused for example by Phakopsorapachyrhizi and Phakopsora meibomiae; Puccinia diseases caused forexample by Puccinia recondita, Puccinia graminis or Pucciniastriiformis; Uromyces diseases caused for example by Uromycesappendiculatus;Oomycete Diseases such as Albugo diseases caused for example by Albugocandida; Bremia diseases caused for example by Bremia lactucae;Peronospora diseases caused for example by Peronospora pisi andPeronospora brassicae; Phytophthora diseases caused for example byPhytophthora infestans;Plasmopara diseases caused for example by Plasmopara viticola;Pseudoperonospora diseases caused for example by Pseudoperonosporahumuli and Pseudoperonospora cubensis; Pythium diseases caused forexample by Pythium ultimum;Leaf spot, Leaf blotch and Leaf Blight Diseases such as Alternariadiseases caused for example by Alternaria solani; Cercospora diseasescaused for example by Cercospora beticola; Cladiosporium diseases causedfor example by Cladiosporium cucumerinum; Cochliobolus diseases causedfor example by Cochliobolus sativus (Conidiaform: Drechslera, Syn:Helminthosporium) or Cochliobolus miyabeanus; Colletotrichum diseasescaused for example by Colletotrichum lindemuthianum; Cycloconiumdiseases caused for example by Cycloconium oleaginum; Diaporthe diseasescaused for example by Diaporthe citri; Elsinoe diseases caused forexample by Elsinoe fawcettii; Gloeosporium diseases caused for exampleby Gloeosporium laeticolor; Glomerella diseases caused for example byGlomerella cingulata; Guignardia diseases caused for example byGuignardia bidwellii; Leptosphaeria diseases caused for example byLeptosphaeria maculans and Leptosphaeria nodorum; Magnaporthe diseasescaused for example by Magnaporthe grisea; Mycosphaerella diseases causedfor example by Mycosphaerella graminicola, Mycosphaerella arachidicolaand Mycosphaerella fijiensis; Phaeosphaeria diseases caused for exampleby Phaeosphaeria nodorum; Pyrenophora diseases caused for example byPyrenophora teres or Pyrenophora tritici repentis; Ramularia-diseasescaused for example by Ramularia collo-cygni or Ramularia areola;Rhynchosporium diseases caused for example by Rhynchosporium secalis;Septoria diseases caused for example by Septoria apii and Septorialycopersici; Typhula diseases caused for example by Thyphula incarnata;Venturia diseases caused for example by Venturia inaequalis;Root-, Sheath and Stem Diseases such as Corticium diseases caused forexample by Corticium graminea-rum; Fusarium diseases caused for exampleby Fusarium oxysporum; Gaeumannomyces diseases caused for example byGaeumannomyces graminis; Rhizoctonia diseases caused for example byRhizoctonia so-lani; Sarocladium diseases caused for example bySarocladium oryzae; Sclerotium diseases caused for ex-ample bySclerotium oryzae; Tapesia diseases caused for example by Tapesiaacuformis; Thielaviopsis dis-eases caused for example by Thielaviopsisbasicola;Ear and Panicle Diseases including Maize cob such as Alternaria diseasescaused for example by Alternaria spp.; Aspergillus diseases caused forexample by Aspergillus flavus; Cladosporium diseases caused for exampleby Cladiosporium cladosporioides; Claviceps diseases caused for exampleby Claviceps pur-purea; Fusarium diseases caused for example by Fusariumculmorum; Gibberella diseases caused for ex-ample by Gibberella zeae;Monographella diseases caused for example by Monographella nivalis;Smut- and Bunt Diseases such as Sphacelotheca diseases caused forexample by Sphacelotheca reiliana; Tilletia diseases caused for exampleby Tilletia caries; Urocystis diseases caused for example by Urocystisocculta; Ustilago diseases caused for example by Ustilago nuda;Fruit Rot and Mould Diseases such as Aspergillus diseases caused forexample by Aspergillus flavus; Bo-trytis diseases caused for example byBotrytis cinerea; Penicillium diseases caused for example byPenicil-lium expansum and Penicillium purpurogenum; Rhizopus diseasescaused by example by Rhizopus stolo-nifer Sclerotinia diseases causedfor example by Sclerotinia sclerotiorum; Verticillium diseases causedfor example by Verticillium alboatrum;Seed- and Soilborne Decay, Mould, Wilt, Rot and Damping-off diseasescaused for example by Alternaria diseases caused for example byAlternaria brassicicola; Aphanomyces diseases caused for example byAphanomyces euteiches; Ascochyta diseases caused for example byAscochyta lentis; Aspergillus diseases caused for example by Aspergillusflavus; Cladosporium diseases caused for example by Cladosporiumherbarum; Cochliobolus diseases caused for example by Cochliobolussativus; (Conidiaform: Drechslera, Bipolaris Syn: Helminthosporium);Colletotrichum diseases caused for example by Colletotrichum coc-codes;Fusarium diseases caused for example by Fusarium culmorum; Gibberelladiseases caused for ex-ample by Gibberella zeae; Macrophomina diseasescaused for example by Macrophomina phaseolina; Microdochium diseasescaused for example by Microdochium nivale; Monographella diseases causedfor ex-ample by Monographella nivalis; Penicillium diseases caused forexample by Penicillium expansum; Phoma diseases caused for example byPhoma lingam; Phomopsis diseases caused for example by Pho-mopsis sojae;Phytophthora diseases caused for example by Phytophthora cactorum;Pyrenophora diseases caused for example by Pyrenophora graminea;Pyricularia diseases caused for example by Pyricularia oryzae; Pythiumdiseases caused for example by Pythium ultimum; Rhizoctonia diseasescaused for exam-ple by Rhizoctonia solani; Rhizopus diseases caused forexample by Rhizopus oryzae; Sclerotium diseases caused for example bySclerotium rolfsii; Septoria diseases caused for example by Septorianodorum; Ty-phula diseases caused for example by Typhula incarnata;Verticillium diseases caused for example by Verticillium dahliae;Canker, Broom and Dieback Diseases such as Nectria diseases caused forexample by Nectria galligena;Blight Diseases such as Monilinia diseases caused for example byMonilinia laxa;Leaf Blister or Leaf Curl Diseases including deformation of blooms andfruits such as Exobasidium diseases caused for example by Exobasidiumvexans.Taphrina diseases caused for example by Taphrina deformans;Decline Diseases of Wooden Plants such as Esca disease caused forexample by Phaeomoniella clamydospora, Phaeoacremonium aleophilum andFomitiporia mediterranea; Ganoderma diseases caused for ex-ample byGanoderma boninense; Rigidoporus diseases caused for example byRigidoporus lignosusDiseases of Flowers and Seeds such as Botrytis diseases caused forexample by Botrytis cinerea;Diseases of Tubers such as Rhizoctonia diseases caused for example byRhizoctonia solani; Helminthospo-rium diseases caused for example byHelminthosporium solani;Club root diseases such as Plasmodiophora diseases, cause for example byPlamodiophora brassicae.

Diseases caused by Bacterial Organisms such as Xanthomonas species forexample Xanthomonas campestris pv. oryzae; Pseudomonas species forexample Pseudomonas syringae pv. lachrymans; Erwinia species for exampleErwinia amylovora.

Fungal diseases on leaves, stems, pods and seeds caused, for example, byalternaria leaf spot (Alternaria spec. atrans tenuissima), anthracnose(Colletotrichum gloeosporoides dematium var. truncatum), brown spot(Septoria glycines), cercospora leaf spot and blight (Cercosporakikuchii), choanephora leaf blight (Choanephora infundibulifera trispora(Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew(Peronospora manshurica), drechslera blight (Drechslera glycini),frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot(Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictasojaecola), pod and stem blight (Phomopsis sojae), powdery mildew(Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines),rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust(Phakopsora pachyrhizi Phakopsora meibomiae), scab (Sphacelomaglycines), stemphylium leaf blight (Stemphylium botryosum), target spot(Corynespora cassiicola).

Fungal diseases on roots and the stem base caused, for example, by blackroot rot (Calonectria crotalariae), charcoal rot (Macrophominaphaseolina), fusarium blight or wilt, root rot, and pod and collar rot(Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusariumequiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris),neocosmospora (Neocosmopspora vasinfecta), pod and stem blight(Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var.caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot(Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythiumirregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum),rhizoctonia root rot, stem decay, and damping off (Rhizoctonia solani),sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia Southernblight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsisbasicola).

Furthermore, the novel compounds of formula I are effective againstphytopathogenic bacteria and viruses (e.g. against Xanthomonas spp,Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaicvirus).

It is also possible to control resistant strains of the organismsmentioned above.

Microorganisms capable of degrading or changing the industrial materialswhich may be mentioned are, for example, bacteria, fungi, yeasts, algaeand slime organisms. The active compounds according to the inventionpreferably act against fungi, in particular moulds, wood-discolouringand wood-destroying fungi (Basidiomycetes) and against slime organismsand algae. Microorganisms of the following genera may be mentioned asexamples: Alternaria, such as Alternaria tenuis, Aspergillus, such asAspergillus niger, Chaetomium, such as Chaetomium globosum, Coniophora,such as Coniophora puetana, Lentinus, such as Lentinus tigrinus,Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporusversicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma,such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride,Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonasaeruginosa, and Staphylococcus, such as Staphylococcus aureus.

The application of the compositions according to the invention ongrowing plants or plant parts, they can also be used to protect plantsor plant parts after harvesting.

Within this application “post-harvest treatment” is to be understood ina very broad sense. On the one hand it means literally the treatment offruit or vegetables after the fruit and vegetables have been harvested.For post-harvest treatment the fruit or vegetable is treated with (e.g.with using the method and apparatus dis-closed in WO 2005/009474),dipped or tank dumped or drenched into a liquid, brushed with,fumigated, painted, fogged (warm or cold), or the fruit may be coatedwith a waxy or other composition. It is also pos-sible to protect plantsor plant parts against post-harvest and storage diseases by applying thecompositions according to the invention shortly before the harvest,while their efficacy persists during transport and storage.

According to the invention, post-harvest and storage diseases may becaused for example by the following fungi: Colletotrichum spp., e.g.Colletotrichum musae, Colletotrichum gloeosporioides, Colletotrichumcoccodes; Fusarium spp., e.g. Fusarium semitectum, Fusarium moniliforme,Fusarium solani, Fusarium ox-ysporum; Verticillium spp., e.g.Verticillium theobromae; Nigrospora spp.; Botrytis spp., e.g. Botrytiscinerea; Geotrichum spp., e.g. Geotrichum candidum; Phomopsis spp.,Phomopsis natalensis; Diplodia spp., e.g. Dip-lodia citri; Alternariaspp., e.g. Alternaria citri, Alternaria alternata; Phytophthora spp.,e.g. Phytophthora citrophthora, Phytophthora fragariae, Phytophthoracactorum, Phytophthora parasitica; Septoria spp., e.g. Sep-toriadepressa; Mucor spp., e.g. Mucor piriformis; Monilinia spp., e.g.Monilinia fructigena, Monilinia laxa; Venturia spp., e.g. Venturiainaequalis, Venturia pyrina; Rhizopus spp., e.g. Rhizopus stolonifer,Rhizopus oryzae; Glomerella spp., e.g. Glomerella cingulata; Sclerotiniaspp., e.g. Sclerotinia fruiticola; Ceratocystis spp., e.g. Ceratocystisparadoxa; Penicillium spp., e.g. Penicillium funiculosum, Penicilliumexpansum, Peni-cillium digitatum, Penicillium italicum; Gloeosporiumspp., e.g. Gloeosporium album, Gloeosporium peren-nans, Gloeosporiumfructigenum, Gloeosporium singulata; Phlyctaena spp., e.g. Phlyctaenavagabunda; Cylindrocarpon spp., e.g. Cylindrocarpon mali; Stemphylliumspp., e.g. Stemphyllium vesicarium; Phacydiopycnis spp., e.g.Phacydiopycnis malirum; Thielaviopsis spp., e.g. Thielaviopsis paradoxy;Aspergillus spp., e.g. Aspergillus niger, Aspergillus carbonarius;Nectria spp., e.g. Nectria galligena; Pezicula spp.

According to the invention, post-harvest storage disorders are forexample scald, scorch, softening, senescent breakdown, lenticel spots,bitter pit, browning, water core, vascular breakdown, CO2 injury, CO2deficiency and O2 deficiency.

Fruit, cutflower and vegetables to be treated according to the inventionare particularly selected from cereals, e.g. wheat, barley, rye, oats,rice, sorghum and the like; beets, e.g. sugar beet and fodder beet; pomeand stone fruit and berries, e.g. apples, pears, plums, peaches,almonds, cherries, strawberries, raspberries and blackberries;leguminous plants, e.g. beans, lentils, peas, soy beans; oleaginousplants, e.g. rape, mus-tard, poppy, olive, sunflower, coconut,castor-oil plant, cocoa, ground-nuts; cucurbitaceae, e.g. pumpkins,gherkins, melons, cucumbers, squashes; fibrous plants, e.g. cotton,flax, hemp, jute; citrus fruit, e.g. orange, lemon, grapefruit,mandarin; tropical fruit, e.g. papaya, passion fruit, mango, carambola,pineapple, ba-nana; vegetables, e.g. spinach, lettuce, asparagus,brassicaceae such as cabbages and turnips, carrots, on-ions, tomatoes,potatoes, hot and sweet peppers; laurel-like plants, e.g. avocado,cinnamon, camphor tree; or plants such as maize, tobacco, nuts, coffee,sugar-cane, tea, grapevines, hops, rubber plants, as well as ornamentalplants, e.g. cutflowers, roses, gerbera and flower bulbs, shrubs,deciduous trees and evergreen trees such as conifers. This enumerationof culture plants is given with the purpose of illustrating theinvention and not to delimiting it thereto.

According to the invention all plants and plant parts can be treated. Byplants is meant all plants and plant populations such as desirable andundesirable wild plants, cultivars and plant varieties (whether or notprotectable by plant variety or plant breeder's rights). Cultivars andplant varieties can be plants obtained by conventional propagation andbreeding methods which can be assisted or supplemented by one or morebiotechnological methods such as by use of double haploids, protoplastfusion, random and directed mutagenesis, molecular or genetic markers orby bioengineering and genetic engineering methods. By plant parts ismeant all above ground and below ground parts and organs of plants suchas shoot, leaf, blossom and root, whereby for example leaves, needles,stems, branches, blossoms, fruiting bodies, fruits and seed as well asroots, tubers, corms and rhizomes are listed. Crops and vegetative andgenerative propagating material, for example cuttings, corms, rhizomes,tubers, runners and seeds also belong to plant parts.

Among the plants that can be protected by the method according to theinvention, mention may be made of major field crops like corn, soybean,cotton, Brassica oilseeds such as Brassica napus (e.g. canola), Brassicarapa, B. juncea (e.g. mustard) and Brassica carinata, rice, wheat,sugarbeet, sugarcane, oats, rye, barley, millet, triticale, flax, vineand various fruits and vegetables of various botanical taxa such asRosaceae sp. (for instance pip fruit such as apples and pears, but alsostone fruit such as apricots, cherries, almonds and peaches, berryfruits such as strawberries), Ribesioidae sp., Juglandaceae sp.,Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceaesp., Actimidaceae sp., Lauraceae sp., Musaceae sp. (for instance bananatrees and plantings), Rubiaceae sp. (for instance coffee), Theaceae sp.,Sterculiceae sp., Rutaceae sp. (for instance lemons, oranges andgrapefruit); Solanaceae sp. (for instance tomatoes, potatoes, peppers,eggplant), Liliaceae sp., Compositiae sp. (for instance lettuce,artichoke and chicory—including root chicory, endive or common chicory),Umbelliferae sp. (for instance carrot, parsley, celery and celeriac),Cucurbitaceae sp. (for instance cucumber—including pickling cucumber,squash, watermelon, gourds and melons), Alliaceae sp. (for instanceonions and leek), Cruciferae sp. (for instance white cabbage, redcabbage, broccoli, cauliflower, brussel sprouts, pak Choi, kohlrabi,radish, horseradish, cress, Chinese cabbage), Leguminosae sp. (forinstance peanuts, peas and beans beans—such as climbing beans and broadbeans), Chenopodiaceae sp. (for instance mangold, spinach beet, spinach,beetroots), Malvaceae (for instance okra), Asparagaceae (for instanceasparagus); horticultural and forest crops; ornamental plants; as wellas genetically modified homologues of these crops.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants ofwhich a heterologous gene has been stably integrated into genome. Theexpression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for example,antisense technology, cosuppression technology or RNAinterference—RNAi—technology). A heterologous gene that is located inthe genome is also called a transgene. A transgene that is defined byits particular location in the plant genome is called a transformationor transgenic event.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the active compounds and compositions which can be usedaccording to the invention, better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, bigger fruits, largerplant height, greener leaf color, earlier flowering, higher qualityand/or a higher nutritional value of the harvested products, highersugar concentration within the fruits, better storage stability and/orprocessability of the harvested products are possible, which exceed theeffects which were actually to be expected.

At certain application rates, the active compound combinations accordingto the invention may also have a strengthening effect in plants.Accordingly, they are also suitable for mobilizing the defense system ofthe plant against attack by unwanted microorganisms. This may, ifappropriate, be one of the reasons of the enhanced activity of thecombinations according to the invention, for example against fungi.Plant-strengthening (resistance-inducing) substances are to beunderstood as meaning, in the present context, those substances orcombinations of substances which are capable of stimulating the defensesystem of plants in such a way that, when subsequently inoculated withunwanted microorganisms, the treated plants display a substantial degreeof resistance to these microorganisms. In the present case, unwantedmicroorganisms are to be understood as meaning phytopathogenic fungi,bacteria and viruses. Thus, the substances according to the inventioncan be employed for protecting plants against attack by theabovementioned pathogens within a certain period of time after thetreatment. The period of time within which protection is effectedgenerally extends from 1 to 10 days, preferably 1 to 7 days, after thetreatment of the plants with the active compounds.

Plants and plant cultivars which are preferably to be treated accordingto the invention include all plants which have genetic material whichimpart particularly advantageous, useful traits to these plants (whetherobtained by breeding and/or biotechnological means).

Plants and plant cultivars which are also preferably to be treatedaccording to the invention are resistant against one or more bioticstresses, i.e. said plants show a better defense against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Examples of nematode resistant plants are described in e.g. U.S. patentapplication Ser. Nos. 11/765,491, 11/765,494, 10/926,819, 10/782,020,12/032,479, 10/783,417, 10/782,096, 11/657,964, 12/192,904, 11/396,808,12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886, 12/364,335,11/763,947, 12/252,453, 12/209,354, 12/491,396 and 12/497,221.

Plants and plant cultivars which may also be treated according to theinvention are those plants which are resistant to one or more abioticstresses. Abiotic stress conditions may include, for example, drought,cold temperature exposure, heat exposure, osmotic stress, flooding,increased soil salinity, increased mineral exposure, ozone exposure,high light exposure, limited availability of nitrogen nutrients, limitedavailability of phosphorus nutrients, shade avoidance.

Plants and plant cultivars which may also be treated according to theinvention, are those plants characterized by enhanced yieldcharacteristics. Increased yield in said plants can be the result of,for example, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including but not limited to, early flowering, floweringcontrol for hybrid seed production, seedling vigor, plant size,internode number and distance, root growth, seed size, fruit size, podsize, pod or ear number, seed number per pod or ear, seed mass, enhancedseed filling, reduced seed dispersal, reduced pod dehiscence and lodgingresistance. Further yield traits include seed composition, such ascarbohydrate content, protein content, oil content and composition,nutritional value, reduction in anti-nutritional compounds, improvedprocessability and better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristic of heterosis or hybrid vigorwhich results in generally higher yield, vigor, health and resistancetowards biotic and abiotic stresses). Such plants are typically made bycrossing an inbred male-sterile parent line (the female parent) withanother inbred male-fertile parent line (the male parent). Hybrid seedis typically harvested from the male sterile plants and sold to growers.Male sterile plants can sometimes (e.g. in corn) be produced bydetasseling, i.e. the mechanical removal of the male reproductive organs(or males flowers) but, more typically, male sterility is the result ofgenetic determinants in the plant genome. In that case, and especiallywhen seed is the desired product to be harvested from the hybrid plantsit is typically useful to ensure that male fertility in the hybridplants is fully restored. This can be accomplished by ensuring that themale parents have appropriate fertility restorer genes which are capableof restoring the male fertility in hybrid plants that contain thegenetic determinants responsible for male-sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedin Brassica species. However, genetic determinants for male sterilitycan also be located in the nuclear genome. Male sterile plants can alsobe obtained by plant biotechnology methods such as genetic engineering.A particularly useful means of obtaining male-sterile plants isdescribed in WO 89/10396 in which, for example, a ribonuclease such asbarnase is selectively expressed in the tapetum cells in the stamens.Fertility can then be restored by expression in the tapetum cells of aribonuclease inhibitor such as barstar.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-resistant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.Plants can be made tolerant to glyphosate through different means. Forexample, glyphosate-tolerant plants can be obtained by transforming theplant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphatesynthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutantCT7) of the bacterium Salmonella typhimurium (Comai et al., 1983,Science 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp.(Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the genesencoding a Petunia EPSPS (Shah et al., 1986, Science 233, 478-481), aTomato EPSPS (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289), or anEleusine EPSPS (WO 01/66704). It can also be a mutated EPSPS.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate oxido-reductase enzyme. Glyphosate-tolerantplants can also be obtained by expressing a gene that encodes aglyphosate acetyl transferase enzyme. Glyphosate-tolerant plants canalso be obtained by selecting plants containing naturally-occurringmutations of the above-mentioned genes. Plants expressing EPSPS genesthat confer glyphosate tolerance are described. Plants comprising othergenes that confer glyphosate tolerance, such as decarboxylase genes, aredescribed.

Other herbicide resistant plants are for example plants that are madetolerant to herbicides inhibiting the enzyme glutamine synthase, such asbialaphos, phosphinothricin or glufosinate. Such plants can be obtainedby expressing an enzyme detoxifying the herbicide or a mutant glutaminesynthase enzyme that is resistant to inhibition. One such efficientdetoxifying enzyme is an enzyme encoding a phosphinothricinacetyltransferase (such as the bar or pat protein from Streptomycesspecies). Plants expressing an exogenous phosphinothricinacetyltransferase are described.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). Hydroxyphenylpyruvatedioxygenases HPPD is an are enzyme thatcatalyze the reaction in which para-hydroxyphenylpyruvate (HPP) istransformed into homogentisate. Plants tolerant to HPPD-inhibitors canbe transformed with a gene encoding a naturally-occurring resistant HPPDenzyme, or a gene encoding a mutated or chimeric HPPD enzyme asdescribed in WO 96/38567, WO 99/24585, and WO 99/24586, WO 2009/144079,WO 2002/046387, or U.S. Pat. No. 6,768,044. Tolerance to HPPD-inhibitorscan also be obtained by transforming plants with genes encoding certainenzymes enabling the formation of homogentisate despite the inhibitionof the native HPPD enzyme by the HPPD-inhibitor. Such plants and genesare described in WO 99/34008 and WO 02/36787. Tolerance of plants toHPPD inhibitors can also be improved by transforming plants with a geneencoding an enzyme having prephenate deshydrogenase (PDH) activity inaddition to a gene encoding an HPPD-tolerant enzyme, as described in WO2004/024928. Further, plants can be made more tolerant to HPPD-inhibitorherbicides by adding into their genome a gene encoding an enzyme capableof metabolizing or degrading HPPD inhibitors, such as the CYP450 enzymesshown in WO 2007/103567 and WO 2008/150473.

Still further herbicide resistant plants are plants that are madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitorsinclude, for example, sulfonylurea, imidazolinone, triazolopyrimidines,pryimidinyoxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides, as described for examplein Tranel and Wright (2002, Weed Science 50:700-712). The production ofsulfonylurea-tolerant plants and imidazolinone-tolerant plants isdescribed. Other imidazolinone-tolerant plants are also described.Further sulfonylurea- and imidazolinone-tolerant plants are alsodescribed.

Other plants tolerant to imidazolinone and/or sulfonylurea can beobtained by induced mutagenesis, selection in cell cultures in thepresence of the herbicide or mutation breeding as described for examplefor soybeans in U.S. Pat. No. 5,084,082, for rice in WO 97/41218, forsugar beet in U.S. Pat. No. 5,773,702 and WO 99/057965, for lettuce inU.S. Pat. No. 5,198,599, or for sunflower in WO 01/065922.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

An “insect-resistant transgenic plant”, as used herein, includes anyplant containing at least one transgene comprising a coding sequenceencoding:

1) an insecticidal crystal protein from Bacillus thuringiensis or aninsecticidal portion thereof, such as the insecticidal crystal proteinslisted by Crickmore et al. (1998, Microbiology and Molecular BiologyReviews, 62: 807-813), updated by Crickmore et al. (2005) at theBacillus thuringiensis toxin nomenclature, online at:http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), orinsecticidal portions thereof, e.g., proteins of the Cry protein classesCry1Ab, Cry1Ac, Cry1B, Cry1C, Cry1D, Cry1F, Cry2Ab, Cry3Aa, or Cry3Bb orinsecticidal portions thereof (e.g. EP 1999141 and WO 2007/107302), orsuch proteins encoded by synthetic genes as e.g. described in U.S.patent application Ser. No. 12/249,016; or2) a crystal protein from Bacillus thuringiensis or a portion thereofwhich is insecticidal in the presence of a second other crystal proteinfrom Bacillus thuringiensis or a portion thereof, such as the binarytoxin made up of the Cry34 and Cry35 crystal proteins (Moellenbeck etal. 2001, Nat. Biotechnol. 19: 668-72; Schnepf et al. 2006, AppliedEnvironm. Microbiol. 71, 1765-1774) or the binary toxin made up of theCry1A or Cry1F proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins(U.S. patent application Ser. No. 12/214,022 and EP 08010791.5); or3) a hybrid insecticidal protein comprising parts of differentinsecticidal crystal proteins from Bacillus thuringiensis, such as ahybrid of the proteins of 1) above or a hybrid of the proteins of 2)above, e.g., the Cry1A.105 protein produced by corn event MON89034 (WO2007/027777); or4) a protein of any one of 1) to 3) above wherein some, particularly 1to 10, amino acids have been replaced by another amino acid to obtain ahigher insecticidal activity to a target insect species, and/or toexpand the range of target insect species affected, and/or because ofchanges introduced into the encoding DNA during cloning ortransformation, such as the Cry3Bb1 protein in corn events MON863 orMON88017, or the Cry3A protein in corn event MIR604; or5) an insecticidal secreted protein from Bacillus thuringiensis orBacillus cereus, or an insecticidal portion thereof, such as thevegetative insecticidal (VIP) proteins listed at:http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html, e.g.,proteins from the VIP3Aa protein class; or6) a secreted protein from Bacillus thuringiensis or Bacillus cereuswhich is insecticidal in the presence of a second secreted protein fromBacillus thuringiensis or B. cereus, such as the binary toxin made up ofthe VIP 1A and VIP2A proteins (WO 94/21795); or7) a hybrid insecticidal protein comprising parts from differentsecreted proteins from Bacillus thuringiensis or Bacillus cereus, suchas a hybrid of the proteins in 1) above or a hybrid of the proteins in2) above; or8) a protein of any one of 5) to 7) above wherein some, particularly 1to 10, amino acids have been replaced by another amino acid to obtain ahigher insecticidal activity to a target insect species, and/or toexpand the range of target insect species affected, and/or because ofchanges introduced into the encoding DNA during cloning ortransformation (while still encoding an insecticidal protein), such asthe VIP3Aa protein in cotton event COT102; or9) a secreted protein from Bacillus thuringiensis or Bacillus cereuswhich is insecticidal in the presence of a crystal protein from Bacillusthuringiensis, such as the binary toxin made up of VIP3 and Cry1A orCry1F (U.S. Patent Appl. No. 61/126,083 and 61/195,019), or the binarytoxin made up of the VIP3 protein and the Cry2Aa or Cry2Ab or Cry2Aeproteins (U.S. patent application Ser. No. 12/214,022 and EP08010791.5).10) a protein of 9) above wherein some, particularly 1 to 10, aminoacids have been replaced by another amino acid to obtain a higherinsecticidal activity to a target insect species, and/or to expand therange of target insect species affected, and/or because of changesintroduced into the encoding DNA during cloning or transformation (whilestill encoding an insecticidal protein)

Of course, an insect-resistant transgenic plant, as used herein, alsoincludes any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 10. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 10, to expand the range oftarget insect species affected when using different proteins directed atdifferent target insect species, or to delay insect resistancedevelopment to the plants by using different proteins insecticidal tothe same target insect species but having a different mode of action,such as binding to different receptor binding sites in the insect.

An “insect-resistant transgenic plant”, as used herein, further includesany plant containing at least one transgene comprising a sequenceproducing upon expression a double-stranded RNA which upon ingestion bya plant insect pest inhibits the growth of this insect pest.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance. Particularly useful stresstolerance plants include:

1) plants which contain a transgene capable of reducing the expressionand/or the activity of poly(ADP-ribose) polymerase (PARP) gene in theplant cells or plants.

2) plants which contain a stress tolerance enhancing transgene capableof reducing the expression and/or the activity of the PARG encodinggenes of the plants or plants cells.

3) plants which contain a stress tolerance enhancing transgene codingfor a plant-functional enzyme of the nicotineamide adenine dinucleotidesalvage synthesis pathway including nicotinamidase, nicotinatephosphoribosyltransferase, nicotinic acid mononucleotide adenyltransferase, nicotinamide adenine dinucleotide synthetase or nicotineamide phosphorybosyltransferase.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage-stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as:

1) transgenic plants which synthesize a modified starch, which in itsphysical-chemical characteristics, in particular the amylose content orthe amylose/amylopectin ratio, the degree of branching, the averagechain length, the side chain distribution, the viscosity behaviour, thegelling strength, the starch grain size and/or the starch grainmorphology, is changed in comparison with the synthesised starch in wildtype plant cells or plants, so that this is better suited for specialapplications.2) transgenic plants which synthesize non starch carbohydrate polymersor which synthesize non starch carbohydrate polymers with alteredproperties in comparison to wild type plants without geneticmodification. Examples are plants producing polyfructose, especially ofthe inulin and levan-type, plants producing alpha-1,4-glucans, plantsproducing alpha-1,6 branched alpha-1,4-glucans, plants producingalternan,3) transgenic plants which produce hyaluronan.4) transgenic plants or hybrid plants, such as onions withcharacteristics such as ‘high soluble solids content’, ‘low pungency’(LP) and/or ‘long storage’ (LS).

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as cotton plants, with altered fibercharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants contain a mutation imparting such alteredfiber characteristics and include:

-   -   a) Plants, such as cotton plants, containing an altered form of        cellulose synthase genes    -   b) Plants, such as cotton plants, containing an altered form of        rsw2 or rsw3 homologous nucleic acids Plants, such as cotton        plants, with increased expression of sucrose phosphate synthase    -   c) Plants, such as cotton plants, with increased expression of        sucrose Plants, such as cotton plants, wherein the timing of the        plasmodesmatal gating at the basis of the fiber cell is altered,        e.g. through downregulation of fiber-selective β-1,3-glucanase    -   d) Plants, such as cotton plants, having fibers with altered        reactivity, e.g. through the expression of        N-acetylglucosaminetransferase gene including nodC and chitin        synthase genes

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered oil profile characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered oil profile characteristics and include:

-   -   a) Plants, such as oilseed rape plants, producing oil having a        high oleic acid content    -   b) Plants such as oilseed rape plants, producing oil having a        low linolenic acid content    -   c) Plant such as oilseed rape plants, producing oil having a low        level of saturated fatty acids

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as potatoes which are virus-resistant,e.g. against potato virus Y (event SY230 and SY233 from Tecnoplant,Argentina), which are disease resistant, e.g. against potato late blight(e.g. RB gene), which show a reduction in cold-induced sweetening(carrying the Nt-Inhh, IIR-INV gene) or which possess a dwarf phenotype(Gene A-20 oxidase).

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered seed shattering characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered seed shattering characteristics andinclude plants such as oilseed rape plants with delayed or reduced seedshattering.

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, orcombination of transformation events, that are the subject of petitionsfor non-regulated status, in the United States of America, to the Animaland Plant Health Inspection Service (APHIS) of the United StatesDepartment of Agriculture (USDA) whether such petitions are granted orare still pending. At any time this information is readily availablefrom APHIS (4700 River Road

Riverdale, Md. 20737, USA), for instance on its interne site (URLhttp://www.aphis.usda.gov/brs/not_reg.html). On the filing date of thisapplication the petitions for nonregulated status that were pending withAPHIS or granted by APHIS were those listed in table B which containsthe following information:

-   -   Petition: the identification number of the petition. Technical        descriptions of the transformation events can be found in the        individual petition documents which are obtainable from APHIS,        for example on the APHIS website, by reference to this petition        number. These descriptions are herein incorporated by reference.    -   Extension of Petition: reference to a previous petition for        which an extension is requested.    -   Institution: the name of the entity submitting the petition.    -   Regulated article: the plant species concerned.    -   Transgenic phenotype: the trait conferred to the plants by the        transformation event.    -   Transformation event or line: the name of the event or events        (sometimes also designated as lines or lines) for which        nonregulated status is requested.    -   APHIS documents: various documents published by APHIS in        relation to the Petition and which can be requested with APHIS.

Additional particularly useful plants containing single transformationevents or combinations of transformation events are listed for examplein the databases from various national or regional regulatory agencies(see for example http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://cera-gmc.org/index.php?evidcode=&hstIDXCode=&gType=&AbbrCode=&atCode=&stCode=&coIDCode=&action=gm_crop_database&mode=Submit).

The compounds of formula (I) are used in unmodified form or, preferably,together with the adjuvants conventionally employed in the art offormulation. To this end they are conveniently formulated in knownmanner to emulsifiable concentrates, coatable pastes, directly sprayableor dilutable solutions, dilute emulsions, wettable powders, solublepowders, dusts, granulates, and also encapsulations e.g. in polymericsubstances.

As with the type of the compositions, the methods of application, suchas spraying, atomising, dusting, scattering, coating or pouring, arechosen in accordance with the intended objectives and the prevailingcircumstances. The compositions may also contain further adjuvants suchas stabilizers, antifoams, viscosity regulators, binders or tackifiersas well as fertilizers, micronutrient donors or other formulations forobtaining special effects.

Suitable carriers and adjuvants can be solid or liquid and aresubstances useful in formulation technology, e.g. natural or regeneratedmineral substances, solvents, dispersants, wetting agents, tackifiers,thickeners, binders or fertilizers. Such carriers are for exampledescribed in WO 97/33890.

The compounds of formula (I) are normally used in the form ofcompositions and can be applied to the crop area or plant to be treated,simultaneously or in succession with further compounds. These furthercompounds can be e.g. fertilizers or micronutrient donors or otherpreparations which influence the growth of plants. They can also beselective herbicides as well as insecticides, fungicides, bactericides,nematicides, molluscicides or mixtures of several of these preparations,if desired together with further carriers, surfactants or applicationpromoting adjuvants customarily employed in the art of formulation.

The compounds of formula (I) can be mixed with other fungicides,resulting in some cases in unexpected synergistic activities. Mixingcomponents which are particularly preferred are azoles, such asazaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole,difenoconazole, diniconazole, epoxiconazole, fenbuconazole,fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil,imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate,penconazole, pyrifenox, prochloraz, propiconazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole,triticonazole; pyrimidinyl carbinole, such as ancymidol, fenarimol,nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol,ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph,spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil,mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil;phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl,ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim,debacarb, fuberidazole, thiabendazole; dicarboximides, such aschlozolinate, dichlozoline, iprodione, myclozoline, procymidone,vinclozoline; carboxamides, such as carboxin, fenfuram, flutolanil,mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine,dodine, iminoctadine; strobilurines, such as azoxystrobin,kresoximmethyl, metominostrobin, SSF-129, trifloxystrobin,picoxystrobin, BAS 500F (proposed name pyraclostrobin), BAS 520;dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb,thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such ascaptafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid;Cu-compounds, such as Bordeaux mixture, copper hydroxide, copperoxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper;nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl;organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane,phosdiphen, pyrazophos, tolclofos-methyl; various others, such asacibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S,chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil,dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, SYP-LI90(proposed name: flumorph), dithianon, ethaboxam, etridiazole,famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam,flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb,IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone,nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb,pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole,triforine, validamycin, zoxamide (RH7281).

A preferred method of applying a compound of formula (I), or anagrochemical composition which contains at least one of said compounds,is foliar application. The frequency of application and the rate ofapplication will depend on the risk of infestation by the correspondingpathogen. However, the compounds of formula I can also penetrate theplant through the roots via the soil (systemic action) by drenching thelocus of the plant with a liquid formulation, or by applying thecompounds in solid form to the soil, e.g. in granular form (soilapplication). In crops of water rice such granulates can be applied tothe flooded rice field. The compounds of formula I may also be appliedto seeds (coating) by impregnating the seeds or tubers either with aliquid formulation of the fungicide or coating them with a solidformulation.

A formulation [that is, a composition containing the compound of formula(I)] and, if desired, a solid or liquid adjuvant, is prepared in a knownmanner, typically by intimately mixing and/or grinding the compound withextenders, for example solvents, solid carriers and, optionally, surfaceactive compounds (surfactants).

The agrochemical formulations will usually contain from 0.1 to 99% byweight, preferably from 0.1 to 95% by weight, of the compound of formulaI, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid orliquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25%by weight, of a surfactant.

Advantageous rates of application are normally from 5 g to 2 kg ofactive ingredient (a. i.) per hectare (ha), preferably from 10 g to 1 kga. i./ha, most preferably from 20 g to 600 g a. i./ha. When used as seeddrenching agent, convenient dosages are from 10 mg to 1 g of activesubstance per kg of seeds.

Whereas it is preferred to formulate commercial products asconcentrates, the end user will normally use dilute formulations.

The following non-limiting Examples illustrate the above-describedinvention in more detail.

Most materials heterocyclic acids and acid halides (compounds accordingto formula (IV) as described above are generally known from theliterature (WO-A 2003/074491 and references cited therein) or may besynthesized according to known methods.

The present invention also relates to a process for the preparation ofspecific difluoromethylpyrazol derivatives according to formula (IVc)and (IVf). Thus according to a further aspect of the present inventionthere is provided a process P1 for the preparation of compounds offormula (IVc) and (IVf) as illustrated by the following reaction schemeP1:

Process P1

5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehydeaccording to formula (IVa) is known from WO-A 2004/014138 (referenceexample 35).

Step 1 of process P1 is performed in the presence of an oxidant, and ifappropriate in the presence of a solvent.

Steps 2 and 5 of process P1 are performed in the presence of acidhalide, and if appropriate in the presence of a solvent.

Step 3 of process P1 is performed in the presence of a fluorinatingagent, and if appropriate in the presence of a solvent.

Step 4 of process P1 is performed in the presence of an acid or a baseand if appropriate in the presence of a solvent

Suitable oxidants for carrying out step of process P1 according to theinvention are in each case all inorganic and organic oxidant which arecustomary for such reactions. Preference is given to usingbenzyltriethylammonium permanganate; bromine; chlorine;m-chloroperbenzoic acid; chromic acid; chromium (VI) oxide; hydrogenperoxide; hydrogen peroxide-boron trifluoride; hydrogen peroxide-urea;2-hydroxyperoxyhexafluoro-2-propanol; Iodine; oxygen-platinum catalyst,perbenzoic acid; peroxyacetyl nitrate; potassium permanganate; potassiumruthenate; pyridinium dichromate; ruthenium (VIII) oxide; silver (I)oxide; silver (II) oxide; silver nitrite; sodium chlorite; sodiumhypochlorite; 2,2,6,6-tetramethylpiperidin-1-oxyl.

Suitable acid halides for carrying out steps 2 and 5 of process P1according to the invention are in each case all organic or inorganicacid halides which are customary for such reactions. Preference is givento using notably phosgene, phosphorous trichloride, phosphorouspentachloride, phosphorous trichloride oxide; thionyl chloride; orcarbon tetrachloride-triphenylphosphine.

Suitable fluorinating agent for carrying out step 3 of process P1according to the invention is in each case all fluorinating agents whichare customary for such reactions. Preference is given to using cesiumfluoride; potassium fluoride; potassium fluoride-calcium difluoride;tetrabutylammonium fluoride.

Suitable solvents for carrying out steps 1 to 5 of process P1 andprocess P2 according to the invention are in each case all customaryinert organic solvents. Preference is given to using optionallyhalogenated aliphatic, alicyclic or aromatic hydrocarbons, such aspetroleum ether, hexane, heptane, cyclohexane, methylcyclohexane,benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene,dichloromethane, chloroform, carbon tetrachloride, dichlorethane ortrichlorethane; ethers, such as diethyl ether, cyclopentyl methylether,diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 2-methyl tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; nitriles, such as acetonitrile,propionitrile, n- or i-butyronitrile or benzonitrile; amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such asmethyl acetate or ethyl acetate, sulphoxides, such as dimethylsulphoxide, or sulphones, such as sulpholane.

When carrying out steps 1 to 5 of process P1 or process P2 according tothe invention, the reaction temperatures can independently be variedwithin a relatively wide range. Generally, processes according to theinvention are carried out at temperatures between 0° C. and 160° C.,preferably between 10° C. and 120° C. A way to control the temperaturefor the processes according to the invention is to use the microwavestechnology.

Steps 1 to 5 of process P1 or process P2 according to the invention aregenerally independently carried out under atmospheric pressure. However,in each case, it is also possible to operate under elevated or reducedpressure.

When carrying out step 1 of process P1 according to the invention,generally 1 mol or other an excess of the oxidant is employed per moleof aldehyde of formula (IVa). It is also possible to employ the reactioncomponents in other ratios.

When carrying out carrying out steps 2 and 5 of process P1 to theinvention, generally 1 mol or other an excess of the acid halides isemployed per mole of acid of formula (IVb) or (IVe). It is also possibleto employ the reaction components in other ratios.

When carrying out steps 3 of process P1 according to the inventiongenerally 1 mol or other an excess of fluorinating agent is employed permole of acid (IVc). It is also possible to employ the reactioncomponents in other ratios.

When carrying out steps 4 of process P1 according to the inventiongenerally 1 mol or other an excess of acid or base is employed per moleof acid halides (IVd). It is also possible to employ the reactioncomponents in other ratios.

Work-up is carried out by customary methods. Generally, the reactionmixture is treated with water and the organic phase is separated offand, after drying, concentrated under reduced pressure. If appropriate,the remaining residue can, be freed by customary methods, such aschromatography, recrystallization or distillation, from any impuritiesthat may still be present.

Compounds according to the invention can be prepared according to theabove described process. It will nevertheless be understood that, on thebasis of his general knowledge and of available publications, theskilled worker will be able to adapt these processes according to thespecifics of each of the compounds according to the invention that isdesired to be synthesized.

The following examples illustrate in a non limiting manner thepreparation and efficacy of the compounds of formula (I) according tothe invention.

Synthesis of5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid(Example IVb)

In a 500 ml flask, 6.0 g (31 mmol) of5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde wereadded to 30 ml of toluene. A solution of 2.4 g (62 mmol) of sodiumhydroxide in 6 ml of water was added to the reaction mixture, followedby 103 ml of a 30% solution of hydrogen peroxide in water, whilstkeeping the temperature below 37° C. After the end of the addition, thereaction mixture was stirred at 50° C. for 7 hours. Once the reactionmixture was back to room temperature, the two phases were separated andthe organic phase was extracted with 100 ml of water. The combinedaqueous phases were acidified to pH 2 with aqueous hydrochloric acid.The resulting white precipitate was filtered, washed two times with 20ml of water, and dried to yield 3.2 g of5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid as awhite solid.

¹H NMR (400 MHz, DMSO-d₆) δ ppm: 3.78 (s, 3H); 7.12 (t, 1H, J_(HF)=53.60Hz) 13.19 (s, 1H);

IR (KBr): 1688 cm⁻¹ (C═O); 2200-3200 cm⁻¹ broad (hydrogen bond);

Synthesis of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonylchloride (Example IVe)

3.2 g of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylicacid and 44.3 ml of thionyl chloride were refluxed for 5 hours. Aftercooling down, the reaction mixture was evaporated under vacuum to yield3.5 g of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonylchloride as a yellow oil.

¹H NMR (400 MHz, CHCl₃-d₆) δ ppm: 3.97 (s, 3H); 7.00 (t, J=52.01 Hz,1H);

IR (TQ): 1759 and 1725 cm⁻¹ (C═O);

Synthesis of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonylfluoride (Example IVd)

To a dried solution of 4.0 g (70 mmol) of potassium fluoride in 21 ml oftetrahydrothiophene-1,1-dioxide was added a solution of 5.0 g (22 mmol)of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloridein 15 ml of toluene at 100° C. The resulting reaction mixture wasstirred at 190-200° C. for 22 hours. Distillation under vacuum yielded 8g of a solution (25% molar) of3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl fluoride intetrahydro-thiophene-1,1-dioxide.

¹H NMR (250 MHz, CHCl₃-d₆) δ ppm: 3.87 (s, 3H); 6.79 (t, J=53.75 Hz,1H);

¹⁹F NMR (250 MHz, CHCl₃-d₆) δ ppm: 45.37 (s, COF); −117.5 (d, J=28.2Hz); −131.6 (m);

Synthesis of5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid(Example IVe)

To 400 ml of a 1N sodium hydroxyde aqueous solution, was added dropwise67.5 g of a solution (10% molar) of3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl fluoride intetrahydrothiophene 1,1-dioxide. The temperature was kept below 20° C.during the addition. After 2 hours of stirring at room temperature, thereaction mixture was carefully acidified to pH 2 with concentratedaqueous hydrochloric acid. The resulting white precipitate was filtered,washed with water, and dried to yield 6 g of5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid as awhite solid.

¹H NMR (400 MHz, DMSO-d₆) δ ppm: 3.90 (s, 3H); 7.22 (t, 1H, J_(HF)=53.55Hz); 13.33 (s, 1H);

Synthesis of 5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonylchloride (Example IVf)

9.1 g of 5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylicacid and 75.5 ml of thionyl chloride were refluxed for 1.5 hours. Aftercooling down, the reaction mixture was evaporated under vacuum to yield10 g of 5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonylchloride as a yellow oil.

GC-MS; observed M/z: Molecular ion: (M^(+.))=212; fragments:(M^(+.)-Cl)=177 and (M^(+.)-F)=193;

Synthesis of 2-[1,1′-Bi(cyclopropyl)-2-yl]cyclohexanamine (Educt forExample 1 and 2)

0.289 g of Ru/C (5%) are added to a solution comprising 3.00 g (17.31mmol) 2-[1,1′-Bi(cyclopropyl)-2-yl]anilin in 20 ml of tetrahydrofuran,and the mixture is hydrogenated with 100 bar of hydrogen at 120° C. for20 hours. After cooling to room temperature, the catalyst is filteredoff through Celite 545 and the product is concentrated under reducedpressure. This gives 3.01 g (96%) of2-[1,1′-Bi(cyclopropyl)-2-yl]cyclohexanamine having a purity of 96%according to MSD-HPLC.

¹H NMR (600 MHz, CD3CN-d) δ ppm: 0.30-0.50 (m, 1H); 0.90-1.00 (m, 1H);1.00-1.40 (m, 1H); 1.50-1.80 (m, 1H)

Example for the formation of compounds according to formula (I) asdescribed in reaction scheme P1 outlined above:

Synthesis ofN-{2-[1,1′-bi(cyclopropyl)-2-yl]cyclohexyl}-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide(Example 1 and 2)

To a mixture of 0.489 g (2.73 mmol)2-[1,1′-bi(cyclopropyl)-2-yl]cyclohexanamine and 0.565 g (4.09 mmol)potassiumcarbonate in 30 ml Acetonitrile was added 0.638 g (3.00 mmol)3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl chloride andstirred at ambient temperature over night. At the end of the reactionthe reaction mixture was extracted with ethylacetate and water. Theorganic layer was dried with natriumsulfate and the solvent was removedby vacuum. The crude product was purified by column chromathography(Solvent: Cyclohexane/ethylacetate gradient). Finally 0.40 g (33%) ofN-{2-[1,1′-bi(cyclopropyl)-2-yl]cyclohexyl}-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamidewith a purity of 87% LC-MS was isolated. log P (acid) of 4.02.

¹H NMR (400 MHz, DMSO-d) δ ppm: 0.1-0.90 (m, 1H); 1.00-1.90 (m, 1H);1.70-1.80 (s, 1H); 7.00-7.40 (m, 1H)

Furtheron the following examples of compounds according to formula (I′)

Are listed in table 1 with the following definitions:

TABLE 1 Ex. A Isomer* 1 3-(difluoromethyl)-5-fluoro-1-methyl-1H- IsomerA pyrazol-4-yl 2 3-(difluoromethyl)-5-fluoro-1-methyl-1H- Isomer B(ex 1) (S) pyrazol-4-yl 3 5-fluoro-1,3-dimethyl-1H-pyrazol-4-yl 45-chloro-3-(difluoromethyl)-1-methyl-1H- pyrazol-4-yl 51-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl Racemic mixture ofenantionmers and diastereomers 62-methyl-4-(trifluoromethyl)-1,3-thiazol-5-yl Racemic misture ofenantionmers and diastereomers 7 2-(trifluoromethyl)phenyl Racemicmixture of enantionmers and diastereomers 8 2-chloropyridin-3-yl 95-fluoro-1,3-dimethyl-1H-pyrazol-4-yl (S) 105-chloro-3-(difluoromethyl)-1-methyl-1H- (S) pyrazol-4-yl 111-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl (S) 122-methyl-4-(trifluoromethyl)-1,3-thiazol-5-yl (S) 132-(trifluoromethyl)phenyl (S) Isomer A of Ex 7 14 2-chloropyridin-3-yl15 4-(difluoromethyl)-2-methyl-1,3-thiazol-5-yl Isomer A 164-(difluoromethyl)-2-methyl-1,3-thiazol-5-yl Isomer B (ex 15) (S) 173-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl (S) 182-(trifluoromethyl)phenyl Isomer B of Ex 7 Isomer A and B do representdifferent isosteromers of the same compound e.g. enantiomers anddiasteromers. *chiral specification in the IUPAC-name at position 1 inthe cyclohexyl-part of the example:

Throughout this description, temperatures are given in degrees Celsius;“NMR” means nuclear magnetic resonance spectrum; and “%” is percent byweight, unless corresponding concentrations are indicated in otherunits.

S=singlet br=broad d=doublet dd=doublet of doublets t=triplet q=quartetm=multiplet ppm=parts per million The NMR peaklist below shows selectedNMR data of table 1,

NMR-Data and Log P-Values of Selected Examples of Table 1

NMR-Peaklist Method

1H-NMR data of the selected examples of table 1 are written in form of1H-NMR-peak lists. To each signal peak are listed the—value in ppm andthe signal intensity:

Example 1

DMSO-d₆

8.5569 (0.32) 7.5977 (0.36) 7.5726 (0.38) 7.5627 (0.39) 7.541 (0.36)7.4122 (0.4) 7.3845 (0.43) 7.3522 (0.87) 7.332 (0.82) 7.2452 (0.49)7.2076 (0.99) 7.1096 (0.98) 7.073 (1.91) 7.0542 (0.73) 7.031 (0.45)6.9748 (0.54) 6.938 (0.99) 6.9192 (0.52) 4.1432 (1.46) 4.1219 (0.57)4.1094 (0.61) 4.0996 (0.56) 4.0568 (1.72) 4.0391 (4.01) 4.0213 (3.81)4.0033 (1.76) 3.8721 (0.46) 3.8068 (1.25) 3.7826 (10.98) 3.7435 (0.4)3.7134 (0.39) 3.6865 (0.41) 3.6776 (0.41) 3.6429 (0.41) 3.62 (0.4)3.4905 (0.81) 3.485 (1.08) 3.4716 (1.6) 3.4669 (1.3) 3.4491 (0.44)3.4034 (0.65) 3.3066 (978.18) 3.2831 (21.01) 3.2387 (0.88) 3.1814 (1.55)3.1639 (0.38) 3.0803 (0.38) 3.0691 (1.32) 2.9909 (5) 2.9687 (0.46)2.9587 (0.48) 2.7855 (0.38) 2.6736 (1.26) 2.6692 (1.59) 2.6647 (1.18)2.6327 (0.33) 2.5222 (7) 2.5089 (86.4) 2.5046 (157.8) 2.5002 (202.58)2.4958 (140.65) 2.4917 (68.34) 2.3311 (1.1) 2.3269 (1.43) 2.3224 (1.07)2.0689 (1.41) 2.0295 (0.42) 1.9867 (16) 1.9075 (0.48) 1.8317 (0.49)1.8227 (0.52) 1.7688 (1.1) 1.7349 (1.23) 1.7066 (1.44) 1.6913 (1.51)1.6384 (2.02) 1.6264 (2.22) 1.5892 (1.61) 1.5486 (1.5) 1.5273 (1.63)1.5013 (2.11) 1.4871 (2.47) 1.476 (2.54) 1.4532 (2.12) 1.4448 (2.05)1.4223 (2.16) 1.4049 (2.22) 1.3984 (3.22) 1.3676 (1.62) 1.3314 (1.43)1.3156 (1.43) 1.2959 (1.89) 1.2659 (1.91) 1.2591 (1.83) 1.236 (1.88)1.1928 (5.48) 1.175 (9.47) 1.1572 (5.32) 1.1077 (0.93) 1.0865 (0.83)1.0713 (0.84) 1.0442 (0.57) 1.0142 (0.37) 0.9889 (0.34) 0.974 (0.34)0.9642 (0.39) 0.9043 (0.95) 0.8894 (1.39) 0.8766 (1.67) 0.8606 (1.58)0.8513 (1.52) 0.8349 (1.76) 0.8215 (1.02) 0.8105 (1.12) 0.7983 (1.05)0.7906 (1.28) 0.7785 (1.27) 0.7661 (1.13) 0.7563 (1.09) 0.7432 (1.09)0.7233 (0.95) 0.7082 (0.9) 0.6976 (1) 0.6883 (0.89) 0.6752 (0.84) 0.6212(0.5) 0.5998 (0.65) 0.5655 (1.01) 0.561 (0.94) 0.5528 (1.23) 0.5418(1.23) 0.532 (1.31) 0.5204 (1.12) 0.5091 (0.99) 0.5018 (0.95) 0.4967(1.07) 0.4584 (1.88) 0.4485 (2.01) 0.4388 (1.99) 0.4261 (1.6) 0.4148(1.53) 0.3853 (2.2) 0.3772 (1.75) 0.3676 (1.67) 0.3417 (1.36) 0.3249(1.62) 0.2984 (1.51) 0.2922 (1.28) 0.288 (1.31) 0.2783 (1.33) 0.272(1.41) 0.2451 (1.5) 0.2352 (1.33) 0.2244 (1.31) 0.2142 (1.44) 0.2026(1.29) 0.193 (1.31) 0.1811 (1.37) 0.1688 (1.21) 0.1576 (1.37) 0.1461(1.65) 0.1344 (1.59) 0.1224 (1.47) 0.1106 (1.5) 0.0992 (1.44) 0.0953(1.44) 0.0869 (1.21) 0.0736 (1.11) 0.0634 (0.99) 0.0505 (0.85) 0.0376(0.86) 0.0078 (2.36) −0.0002 (29.16) −0.0086 (2.16) −0.0142 (1.55)−0.0271 (2.26) −0.0403 (2.67) −0.0538 (2.05) −0.0985 (0.39) −0.1124(0.35) −0.124 (0.38) −0.1308 (0.4) −0.1495 (0.41)

Log P^([b])=4.02

Example 2

DMSO-d₆

7.5946 (0.49) 7.5611 (1.37) 7.5386 (1.46) 7.3478 (0.39) 7.3255 (0.41)7.2449 (1.68) 7.216 (0.41) 7.2103 (0.55) 7.1544 (0.39) 7.1101 (3.7)7.0809 (0.89) 7.0756 (1.22) 6.9754 (1.9) 6.9458 (0.49) 6.9409 (0.66)3.8056 (1.55) 3.7831 (16) 3.6675 (0.51) 3.657 (0.49) 3.6412 (0.82)3.6181 (0.83) 3.5928 (0.43) 3.3052 (288.59) 2.6738 (0.45) 2.6693 (0.56)2.6646 (0.46) 2.5223 (2.75) 2.5089 (30.03) 2.5047 (53.84) 2.5002 (68.38)2.4959 (47.25) 2.3314 (0.42) 2.3269 (0.54) 2.3223 (0.39) 2.0692 (0.57)2.0343 (0.41) 1.7683 (1.77) 1.7404 (2.19) 1.7089 (1.42) 1.6455 (2.68)1.6263 (2.15) 1.5516 (0.44) 1.5011 (0.77) 1.4763 (0.86) 1.4469 (0.72)1.4295 (0.61) 1.421 (0.69) 1.3994 (0.69) 1.3829 (0.59) 1.3549 (0.6)1.3171 (0.85) 1.2953 (1.4) 1.2615 (1.49) 1.2419 (2.03) 1.2225 (2.07)1.1962 (1.1) 1.1642 (0.95) 1.1466 (1.18) 1.133 (1.07) 1.1077 (1.34)1.0861 (1.66) 1.0677 (1.73) 1.0385 (0.8) 1.0093 (0.32) 0.9052 (0.43)0.8775 (2.01) 0.8614 (1.99) 0.8516 (0.74) 0.8451 (0.5) 0.8351 (0.72)0.8183 (0.35) 0.7877 (0.51) 0.7753 (0.81) 0.7639 (1.07) 0.7546 (1.44)0.7433 (1.62) 0.7344 (1.15) 0.723 (1.28) 0.7101 (0.88) 0.6974 (1.1)0.6755 (0.98) 0.6499 (0.44) 0.5825 (0.52) 0.5791 (0.54) 0.5674 (0.65)0.5519 (0.62) 0.5449 (0.52) 0.5312 (0.58) 0.5185 (0.54) 0.5104 (0.43)0.4974 (0.49) 0.4698 (1.25) 0.46 (1.99) 0.4496 (2.33) 0.4393 (2.66)0.4279 (2.06) 0.4164 (1.29) 0.3979 (1.79) 0.3876 (2.9) 0.3768 (2.16)0.3665 (1.88) 0.3553 (1.11) 0.3459 (1.14) 0.3419 (1.09) 0.3255 (1.06)0.3102 (0.68) 0.3065 (0.72) 0.2982 (1.05) 0.2877 (1.59) 0.2835 (1.58)0.2793 (1.85) 0.2688 (2.23) 0.2626 (2.1) 0.2586 (1.97) 0.2531 (2.1)0.2488 (2.16) 0.2454 (2.03) 0.2414 (1.64) 0.2379 (1.64) 0.2264 (1.35)0.2152 (1.21) 0.2044 (0.6) 0.1813 (0.44) 0.1679 (1.38) 0.1573 (1.98)0.1459 (2.08) 0.1353 (1.63) 0.124 (1.15) 0.1117 (0.96) 0.0996 (0.88)0.0952 (0.93) 0.0868 (0.8) 0.0826 (0.79) 0.074 (0.72) 0.0641 (0.5)0.0598 (0.55) 0.0512 (0.43) 0.0078 (1.61) −0.0002 (14.28) −0.0086 (1.09)−0.0236 (1.13) −0.0335 (1.57) −0.0421 (2.28) −0.0458 (2.24) −0.0501(1.78) −0.0546 (2.17) −0.0586 (2.15) −0.063 (1.96) −0.0674 (1.55)−0.0712 (1.2) −0.0762 (1.43) −0.08 (0.97) −0.0889 (0.66) −0.099 (0.41)

Log P^([b])=3.84

Example 3

DMSO-d₆

17.143 (1.82) 12.9084 (1.73) 11.8878 (1.65) 10.4516 (1.7) 7.1746 (1.58)4.6724 (1.62) 4.0736 (1.66) 4.0444 (1.89) 3.9636 (1.94) 3.939 (2.1)3.9252 (1.76) 3.915 (1.76) 3.8709 (1.72) 3.8503 (1.71) 3.8239 (2.1)3.7951 (2.34) 3.7736 (1.83) 3.7384 (2.18) 3.7318 (2.45) 3.6729 (2.74)3.6588 (3.03) 3.6379 (6.8) 3.6236 (10) 3.5929 (2.92) 3.5634 (3.22)3.5568 (3.01) 3.5428 (3.88) 3.4832 (4.52) 3.4725 (4.86) 3.4543 (5.1)3.4276 (7.01) 3.4167 (7.3) 3.2789 (172.82) 3.2392 (3.96) 3.2233 (2.75)3.1953 (1.72) 2.719 (1.84) 2.7076 (2.17) 2.6984 (2.26) 2.6734 (12.47)2.669 (16) 2.6646 (12.2) 2.6442 (3.39) 2.6158 (3.41) 2.5389 (191.96)2.5086 (920.07) 2.5043 (1696.22) 2.4998 (2192.31) 2.4954 (1505.29) 2.491(708.35) 2.4192 (1.84) 2.3311 (10.26) 2.3266 (13.69) 2.3219 (9.62)2.2408 (6.8) 2.2204 (9.16) 2.0692 (15.55) 1.7732 (1.77) 1.6698 (1.65)1.6426 (1.88) 1.6349 (2.2) 1.6049 (1.67) 1.2342 (5.11) 1.2083 (2.53)1.2036 (2.57) 1.0639 (2.21) 1.06 (1.89) 0.7222 (1.7) 0.2712 (1.76)0.2508 (1.71) 0.2458 (1.9) 0.1515 (2.49) 0.1458 (6.52) 0.1139 (1.63)0.087 (1.88) 0.0079 (65.62) −0.0002 (1338.36) −0.0085 (51.19) −0.0414(2.57) −0.0558 (1.84) −0.1494 (5.95)

Log P^([b])=3.35

Example 5

DMSO-d₆

8.3021 (3.64) 8.2862 (0.81) 8.2575 (0.6) 8.2304 (0.53) 8.2087 (3.19)7.903 (0.33) 7.8805 (0.45) 7.8652 (0.36) 7.8385 (1.43) 7.8164 (1.64)7.8078 (1.69) 7.7838 (1.28) 7.6453 (0.34) 4.1151 (0.34) 4.1062 (0.36)4.0514 (0.33) 4.0128 (0.43) 3.9996 (0.49) 3.9491 (15.4) 3.9299 (16)3.8945 (0.4) 3.8772 (0.33) 3.8582 (0.39) 3.8441 (0.36) 3.8323 (0.35)3.808 (0.4) 3.7715 (0.56) 3.7613 (0.51) 3.7479 (0.57) 3.7256 (0.49)3.7175 (0.49) 3.7115 (0.49) 3.6853 (0.79) 3.6576 (1.31) 3.6452 (1.23)3.635 (1.71) 3.6085 (1.31) 3.5078 (0.87) 3.4628 (1.07) 3.459 (1.06)3.4434 (1.24) 3.388 (2.3) 3.3048 (3501.04) 3.2811 (36.88) 2.795 (0.33)2.7101 (0.58) 2.6734 (2.48) 2.669 (3.11) 2.6647 (2.36) 2.6372 (0.59)2.6239 (0.71) 2.5391 (87.31) 2.5088 (178.89) 2.5044 (334.85) 2.4999(439.78) 2.4955 (306.74) 2.4911 (148.29) 2.4191 (0.38) 2.3635 (0.36)2.3312 (2.15) 2.3267 (2.74) 2.3222 (2.04) 2.0692 (3.89) 1.8015 (0.54)1.745 (2.75) 1.7358 (2.7) 1.6838 (1.76) 1.6533 (3.07) 1.6281 (2) 1.5787(0.35) 1.5544 (0.36) 1.3768 (0.39) 1.3542 (0.36) 1.333 (0.35) 1.3041(0.63) 1.298 (0.68) 1.282 (0.94) 1.2367 (2.5) 1.2135 (2.01) 1.2054(2.08) 1.1866 (1.89) 1.1565 (1.82) 1.1264 (1.32) 1.082 (2.31) 1.0693(2.55) 1.0389 (1.25) 0.9291 (0.35) 0.9134 (0.39) 0.9001 (0.97) 0.8895(1.2) 0.8767 (1.08) 0.8667 (1.1) 0.8543 (0.7) 0.7733 (0.43) 0.7595(0.67) 0.7512 (0.96) 0.7403 (0.99) 0.7299 (0.66) 0.7196 (0.49) 0.7003(0.37) 0.6596 (1.55) 0.6466 (1.49) 0.6374 (2.38) 0.6265 (2.36) 0.6165(1.61) 0.6071 (1.58) 0.5864 (0.66) 0.5655 (0.39) 0.5179 (0.37) 0.4929(0.35) 0.456 (0.74) 0.4447 (1.05) 0.4341 (1.52) 0.4233 (1.52) 0.4149(1.33) 0.4041 (1.42) 0.3945 (1.41) 0.3872 (0.72) 0.3729 (0.57) 0.3578(0.4) 0.3139 (1.06) 0.2923 (1.15) 0.2739 (1.43) 0.2684 (1.45) 0.2614(1.94) 0.2484 (1.73) 0.2406 (1.99) 0.2287 (1.92) 0.218 (1.8) 0.2063(1.7) 0.1946 (1.08) 0.1836 (0.81) 0.1717 (0.52) 0.1463 (0.51) 0.132(0.97) 0.1224 (1.33) 0.1117 (1.43) 0.0952 (1.26) 0.0869 (1.22) 0.0818(1.33) 0.0744 (1.6) 0.0692 (1.3) 0.0616 (1.87) 0.0546 (1.27) 0.0491(1.79) 0.0378 (1.22) 0.0285 (1.3) 0.0079 (3.86) −0.0002 (64.29) −0.0084(3.3) −0.0166 (2.44) −0.0238 (1.97) −0.0314 (2.05) −0.0376 (2.26)−0.0511 (2.12) −0.0637 (1.69) −0.0678 (1.88) −0.0718 (1.83) −0.0852(1.54) −0.0962 (0.77) −0.1076 (0.61) −0.1322 (0.47) −0.1541 (1.06)−0.1667 (1.25) −0.1753 (1.42) −0.1874 (0.85) −0.1992 (0.8) −0.2116(1.29) −0.2209 (1.4) −0.2247 (1.14) −0.2327 (0.84) −0.2482 (0.52)−0.3227 (0.43) −2.8999 (0.32) −3.0829 (0.37)

Log P^([b])=3.61

Example 6

CD₃CN

2.7001 (2.53) 2.6907 (1.85) 2.5149 (16) 2.2989 (23.27) 1.9534 (0.9)1.9493 (1.64) 1.9452 (2.39) 1.9411 (1.64) 1.937 (0.83) 0.9226 (0.42)−0.0002 (0.79)

Log P^([b])=4.14

Example 7

CD₃CN

7.7573 (6.09) 7.7565 (6.62) 7.7557 (6.2) 7.7426 (12.09) 7.7337 (1.83)7.7286 (6.42) 7.6925 (2.29) 7.6916 (2.29) 7.6798 (6.62) 7.6729 (3.24)7.6719 (3.16) 7.6677 (6.14) 7.6667 (5.89) 7.6603 (7.02) 7.6594 (6.65)7.6476 (11.52) 7.6465 (12.11) 7.6348 (4.11) 7.6338 (4.19) 7.6123 (3.19)7.611 (4.12) 7.6099 (3.81) 7.6087 (3.03) 7.5976 (8.44) 7.5964 (8.03)7.5844 (6.36) 7.5831 (6.85) 7.5766 (0.66) 7.5716 (1.72) 7.5701 (2.14)7.5283 (5.5) 7.5275 (5.95) 7.5159 (4.64) 7.5149 (5.03) 7.4831 (1.25)7.4705 (1.08) 6.724 (1.84) 6.7119 (1.97) 6.6794 (1.78) 6.6657 (1.58)3.7905 (1.13) 3.7838 (1.21) 3.7749 (1.46) 3.7721 (1.93) 3.7684 (1.69)3.766 (1.95) 3.7568 (3.22) 3.7543 (2) 3.7501 (3.35) 3.742 (1.87) 3.7389(3.79) 3.7354 (2.21) 3.7323 (3.68) 3.7243 (2.52) 3.7213 (2.02) 3.7177(2.61) 3.7147 (1.75) 3.7067 (1.48) 3.6999 (1.39) 3.6033 (0.41) 3.5966(0.43) 3.5874 (0.48) 3.5812 (0.45) 3.2762 (0.36) 3.2677 (0.36) 2.5074(6.23) 2.2571 (1.01) 2.2315 (896.74) 2.2075 (1.55) 2.0573 (0.48) 2.0532(0.73) 2.0491 (0.51) 2.002 (0.81) 1.996 (2.11) 1.9935 (2.23) 1.9899(2.34) 1.9873 (2.33) 1.981 (1.71) 1.9747 (2.36) 1.9723 (2.52) 1.9669(5.89) 1.9588 (4.29) 1.9547 (4.77) 1.9508 (44.96) 1.9468 (87.64) 1.9427(126.66) 1.9386 (82.88) 1.9344 (41.23) 1.9298 (1.85) 1.9255 (1.56)1.9227 (1.98) 1.9203 (1.98) 1.9167 (1.96) 1.9142 (2.01) 1.9105 (1.01)1.9079 (1.43) 1.905 (1.03) 1.9016 (1.94) 1.8992 (2.07) 1.8955 (2.04)1.8931 (1.97) 1.887 (0.77) 1.8788 (0.46) 1.8756 (0.5) 1.8732 (0.49) 1.87(0.47) 1.8569 (0.45) 1.8536 (0.51) 1.8514 (0.49) 1.848 (0.46) 1.8361(0.44) 1.832 (0.68) 1.8279 (1.29) 1.8237 (1.42) 1.8196 (1.59) 1.8171(1.98) 1.8135 (1.94) 1.8113 (1.81) 1.8067 (2.03) 1.7971 (3.63) 1.7912(3.31) 1.7875 (3.04) 1.7854 (2.94) 1.781 (3.07) 1.7744 (2.94) 1.7714(2.59) 1.7684 (1.7) 1.7655 (1.91) 1.761 (0.89) 1.7572 (0.62) 1.7532(0.73) 1.7456 (0.91) 1.7399 (0.89) 1.7361 (1.1) 1.7306 (1) 1.7267 (1.49)1.7238 (2.02) 1.7211 (2.38) 1.7181 (3.13) 1.7125 (3.26) 1.7097 (3.13)1.7072 (3.58) 1.7017 (4) 1.6957 (4.72) 1.6909 (5.7) 1.6871 (5.77) 1.6851(5.67) 1.6827 (6.08) 1.6791 (5.62) 1.6734 (4.61) 1.6704 (4.34) 1.6672(4.21) 1.664 (4.49) 1.6615 (3.82) 1.6581 (2.77) 1.6555 (2.25) 1.6495(0.76) 1.6461 (0.55) 1.6397 (0.4) 1.3861 (0.5) 1.3843 (0.57) 1.3783(0.94) 1.3735 (0.96) 1.3685 (1.23) 1.3628 (2.21) 1.3568 (2.93) 1.3521(2.67) 1.3471 (3.1) 1.3415 (3.24) 1.3358 (3.44) 1.3303 (3.31) 1.3265(2.75) 1.3213 (2.53) 1.315 (1.81) 1.3111 (1.55) 1.3089 (1.61) 1.3053(1.44) 1.2975 (0.74) 1.2897 (0.83) 1.2821 (0.67) 1.2766 (0.66) 1.2729(1.07) 1.27 (1.39) 1.265 (0.77) 1.2616 (1.07) 1.2575 (1.17) 1.2541(0.86) 1.2479 (0.82) 1.2453 (0.67) 1.2413 (0.89) 1.2367 (0.53) 1.2326(0.8) 1.2301 (0.95) 1.2263 (1.01) 1.2194 (0.51) 1.2106 (0.9) 1.2051(2.04) 1.1991 (2.76) 1.1936 (2.39) 1.1837 (4.46) 1.179 (7.14) 1.1724(5.52) 1.1662 (7.84) 1.1617 (8.66) 1.1599 (9.5) 1.1535 (10.37) 1.1476(10.7) 1.1429 (6.07) 1.1387 (5.69) 1.1329 (5.69) 1.1266 (5.08) 1.1173(0.63) 1.1125 (1.89) 1.1061 (1.08) 1.1009 (0.68) 1.0742 (0.4) 1.0683(0.4) 1.0553 (0.36) 1.0525 (0.64) 1.0497 (0.43) 1.0467 (0.57) 1.0338(0.48) 1.0308 (0.4) 1.028 (0.48) 0.8986 (1.3) 0.8912 (3.78) 0.8838(5.31) 0.8813 (2.95) 0.8791 (3.65) 0.8765 (6.26) 0.8727 (4.31) 0.8677(6.08) 0.8654 (3.36) 0.8624 (2.94) 0.86 (4.21) 0.8548 (3.06) 0.8526(1.66) 0.8471 (2.1) 0.8391 (0.83) 0.8162 (0.68) 0.808 (1.96) 0.8025(1.61) 0.7998 (2.19) 0.7944 (4.13) 0.7917 (1.23) 0.7889 (1.23) 0.7862(4.33) 0.7808 (2.33) 0.778 (1.8) 0.7727 (2.26)

Log P^([b])=4.11

Example 13

Isomer A

Log P^([b])=4.17

M+H=352.19

Example 15

Log P^([b])=4.31

M+H=357.30

Example 18

Isomer B

Log P^([b])=4.23

M+H=352.24

Intensity of sharp signals correlates with the height of the signals ina printed example of a NMR spectrum in cm and shows the real relationsof signal intensities. From broad signals several peaks or the middle ofthe signal and their relative intensity in comparison to the mostintensive signal in the spectrum can be shown

The 1H-NMR peak lists are similar to classical 1H-NMR prints and containtherefore usually all peaks, which are listed at classicalNMR-interpretation.

Additionally they can show like classical 1H-NMR prints signals ofsolvents, stereoisomers of the target compounds, which are also objectof the invention, and/or peaks of impurities.

To show compound signals in the delta-range of solvents and/or water theusual peaks of solvents, for example peaks of DMSO in DMSO-d6 and thepeak of water are shown in our 1H-NMR peak lists and have usually onaverage a high intensity.

The peaks of stereoisomers of the target compounds and/or peaks ofimpurities have usually on average a lower intensity than the peaks oftarget compounds (for example with a purity >90%).

Such stereoisomers and/or impurities can be typical for the specificpreparation process. Therefore their peaks can help to recognize thereproduction of our preparation process via“side-products-fingerprints”.

An expert, who calculates the peaks of the target compounds with knownmethods (MestreC, ACD-simulation, but also with empirically evaluatedexpectation values) can isolate the peaks of the target compounds asneeded optionally using additional intensity filters. This isolationwould be similar to relevant peak picking at classical 1H-NMRinterpretation.

Measurement of log P values was performed according EEC directive 79/831Annex V.A8 by HPLC (High Performance Liquid Chromatography) on reversedphase columns with the following methods:

^([b]) measurement of LC-MS was done at pH 2.7 with 0.1% formic acid inwater and with acetonitrile (contains 0.1% formic acid) as eluent with alinear gradient from 10% acetonitrle to 95% acetonitrile.

Calibration was done with not branched alkan2-ones (with 3 to 16 carbonatoms) with known log P-values (measurement of log P values usingretention times with linear interpolation between successive alkanones).lambda-maX-values were determined using UV-spectra from 200 nm to 400 nmand the peak values of the chromatographic signals.

In table 1, M+H (or M H) means the molecular ion peak, plus or minus 1a.m.u. (atomic mass unit) respectively, as observed in mass spectroscopyand M (ApcI+) means the molecular ion peak as it was found via positiveatmospheric pressure chemical ionisation in mass spectroscopy.

Example Sphaerotheca Test (Cucumber)/Preventive

Solvent: 49 parts by weight of N,N-Dimethylformamide Emulsifier: 1 partby weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Sphaerotheca fuliginea. Then the plants are placedin a greenhouse at approximately 23° C. and a relative atmospherichumidity of approximately 70%.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of 70% or even higher at a concentration of 500 ppm of activeingredient.

Example # Eff. % 1 100 2 100 3 95 4 100 5 90 6 94 7 78

Example Alternaria Test (Tomato)/Preventive

Solvent: 49 parts by weight of N,N-Dimethylformamide Emulsifier: 1 partby weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Alternaria solani. The plants remain for one day inan incubation cabinet at approximately 22° C. and a relative atmospherichumidity of 100%. Then the plants are placed in an incubation cabinet atapproximately 20° C. and a relative atmospheric humidity of 96%.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of 70% or even higher at a concentration of 500 ppm of activeingredient.

Example # Eff. % 1 100 2 100 3 94 4 95 5 94 6 94

Example Pyrenophora Test (Barley)/Preventive

Solvent: 49 parts by weight of N,N-Dimethylformamide Emulsifier: 1 partby weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Pyrenophora teres. The plants remain for 48 hours inan incubation cabinet at 22° C. and a relative atmospheric humidity of100%. Then the plants are placed in a greenhouse at a temperature ofapproximately 20° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 7-9 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of 70% or even higher at a concentration of 500 ppm of activeingredient.

Example # Eff. % 1 100 2 100 3 100 4 80 5 95 6 100 8 90 7 90

Example Podosphaera Test (Apples)/Preventive

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Afterthe spray coating has dried on, the plants are inoculated with anaqueous spore suspension of the causal agent of apple mildew(Podosphaera leucotricha). The plants are then placed in a greenhouse atapproximately 23° C. and a relative atmospheric humidity ofapproximately 70%.

The test is evaluated 10 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control, while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of 70% or even higher at a concentration of 100 ppm of activeingredient.

Example # Eff. % 1 100 2 100

Example Venturia Test (Apples)/Preventive

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Afterthe spray coating has dried on, the plants are inoculated with anaqueous conidia suspension of the causal agent of apple scab (Venturiainaequalis) and then remain for 1 day in an incubation cabinet atapproximately 20° C. and a relative atmospheric humidity of 100%.

The plants are then placed in a greenhouse at approximately 21° C. and arelative atmospheric humidity of approximately 90%.

The test is evaluated 10 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control, while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of 70% or even higher at a concentration of 100 ppm of activeingredient.

Example # Eff. % 1 100 2 100

Example Blumeria Test (Barley)/Preventive

Solvent: 49 parts by weight of n,n-dimethylacetamid Emulsifier: 1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are dusted withspores of Blumeria graminis f. sp. hordei.

The plants are placed in the greenhouse at a temperature ofapproximately 18° C. and a relative atmospheric humidity ofapproximately 80% to promote the development of mildew pustules.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedan efficacy of 70% or even higher at a concentration of 500 ppm ofactive ingredient.

Example # Eff. % 1 100 2 100

Example Septoria tritici-Test (Wheat)/Preventive

Solvent: 49 parts by weight of n,n-dimethylacetamid Emulsifier: 1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are sprayed with aspore suspension of Septoria tritici. The plants remain for 48 hours inan incubation cabinet at approximately 20° C. and a relative atmospherichumidity of approximately 100% and afterwards for 60 hours atapproximately 15° C. in a translucent incubation cabinet at a relativeatmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature ofapproximately 15° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 21 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control, while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedan efficacy of 70% or even higher at a concentration of 500 ppm ofactive ingredient.

Example # Eff. % 1 90 2 90

Example

Puccinia triticina-Test (Wheat)/Preventive

Solvent: 49 parts by weight of n,n-dimethylacetamid Emulsifier: 1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are sprayed with aspore suspension of Puccinia triticina. The plants remain for 48 hoursin an incubation cabinet at approximately 20° C. and a relativeatmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature ofapproximately 20° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 8 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedan efficacy of 70% or even higher at a concentration of 500 ppm ofactive ingredient.

Example # Eff. % 1 100 2 100

Example Fusarium nivale (var. majus)-Test (Wheat)/Preventive

Solvent: 49 parts by weight of n,n-dimethylacetamid Emulsifier: 1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are slightly injuredby using a sandblast and afterwards they are sprayed with a conidiasuspension of Fusarium nivale (var. majus).

The plants are placed in the greenhouse under a translucent incubationcabinet at a temperature of approximately 10° C. and a relativeatmospheric humidity of approximately 100%.

The test is evaluated 5 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedan efficacy of 70% or even higher at a concentration of 500 ppm ofactive ingredient.

Example # Eff. % 1 100 2 100

The invention claimed is:
 1. A compound of formula (I)

in which R¹ represents hydrogen, fluoro, chloro or bromo; R² representshydrogen fluoro, chloro or bromo; R³ represents optionally substitutedC₂₋₁₂ alkyl, optionally substituted C₂₋₁₂ alkenyl, optionallysubstituted C₂₋₁₂ alkynyl, optionally substituted C₃₋₁₂ cycloalkyl,optionally substituted phenyl or optionally substituted heterocyclyl; Arepresents one of the radicals A1 to A18 below

R¹⁸ represents hydrogen, cyano, halogen, nitro, C₁-C₄-alkyl,C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, C₁-C₄-haloalkyl,C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in each case 1 to 5halogen atoms, aminocarbonyl or aminocarbonyl-C₁-C₄-alkyl, R¹⁹represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy orC₁-C₄-alkylthio, R²⁰ represents hydrogen, C₁-C₄-alkyl,hydroxy-C₁-C₄-alkyl, C₂-C₆-alkenyl, C₃-C₆-cycloalkyl,C₁-C₄-alkylthio-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-haloalkylthio-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl having ineach case 1 to 5 halogen atoms, or phenyl, R²¹ and R²² independently ofone another represent hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkylhaving 1 to 5 halogen atoms, R²³ represents halogen, cyano orC₁-C₄-alkyl, or C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy having in each case1 to 5 halogen atoms, R²⁴ and R²⁵ independently of one another representhydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogenatoms, R²⁶ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkylhaving 1 to 5 halogen atoms, R²⁷ represents hydrogen, halogen, hydroxyl,cyano, C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy orC₁-C₄-haloalkylthio having in each case 1 to 5 halogen atoms, R²⁸represents halogen, hydroxyl, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio orC₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, R²⁹represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy having in each case 1to 5 halogen atoms, C₁-C₄-alkylsulphinyl or C₁-C₄-alkylsulphonyl, R³⁰represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms,R³¹ represents C₁-C₄-alkyl, Q¹ represents S (sulphur), SO, SO₂ or CH₂, prepresents 0, 1 or 2, where R³¹ represents identical or differentradicals if p represents 2, R³² represents C₁-C₄-alkyl orC₁-C₄-haloalkyl having 1 to 5 halogen atoms, R³³ represents C₁-C₄-alkylor C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R³⁴ and R³⁵independently of one another represent hydrogen, halogen, amino,C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R³⁶represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to5 halogen atoms, R³⁷ and R³⁸ independently of one another representhydrogen, halogen, amino, nitro, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1to 5 halogen atoms, R³⁹ represents hydrogen, halogen, C₁-C₄-alkyl orC₁-C₄-haloalkyl having 1 to 5 halogen atoms, R⁴⁰ represents hydrogen,halogen, amino, C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)amino, cyano,C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R⁴¹represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogenatoms, R⁴² represents hydrogen, halogen, amino, C₁-C₄-alkylamino,di-(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to5 halogen atoms, R⁴³ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkylhaving 1 to 5 halogen atoms, R⁴⁴ represents halogen, C₁-C₄-alkyl orC₁-C₄-haloalkyl having 1 to 5 halogen atoms, R⁴⁵ represents hydrogen orC₁-C₄-alkyl, R⁴⁶ represents halogen or C₁-C₄-alkyl, R⁴⁷ representsC₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R⁴⁸represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to5 halogen atoms, R⁴⁹ represents halogen, hydroxyl, C₁-C₄-alkyl,C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio orC₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, R⁵⁰represents C₁-C₄-alkyl.
 2. A compound of formula (I) as claimed in claim1, wherein R¹ and R² are, independently, hydrogen or fluoro; R³ is C₂₋₆alkyl, optionally substituted C₃₋₈ cycloalkyl, phenyl, thienyl or furyl;A represents one of the radicals A1, A2, A3, A4, A5, A6, A9, A10, A11,A12 or A17; R¹⁸ represents hydrogen, cyano, fluorine, chlorine, bromine,iodine, methyl, ethyl, isopropyl, methoxy, ethoxy, methylthio,ethylthio, cyclopropyl, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy having in eachcase 1 to 5 fluorine, chlorine and/or bromine atoms,trifluoromethylthio, difluoromethylthio, aminocarbonyl,aminocarbonylmethyl or aminocarbonylethyl; R¹⁹ represents hydrogen,fluorine, chlorine, bromine, iodine, methyl, ethyl, methoxy, ethoxy,methylthio or ethylthio; R²⁰ represents hydrogen, methyl, ethyl,n-propyl, isopropyl, C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorineand/or bromine atoms, hydroxymethyl, hydroxyethyl, cyclopropyl,cyclopentyl, cyclohexyl or phenyl; R²¹ and R²² independently of oneanother represent hydrogen, fluorine, chlorine, bromine, methyl, ethylor C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromineatoms; R²³ represents fluorine, chlorine, bromine, cyano, methyl, ethyl,C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy having in each case 1 to 5 fluorine,chlorine and/or bromine atoms; R²⁴ and R²⁵ independently of one anotherrepresent hydrogen, fluorine, chlorine, bromine, methyl, ethyl orC₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine atoms;R²⁶ represents hydrogen, fluorine, chlorine, bromine, iodine, methyl,ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromineatoms; R²⁷ represents hydrogen, fluorine, chlorine, bromine, iodine,hydroxyl, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, difluoromethyl, trifluoromethyl,difluorochloromethyl, trichloromethyl, trifluoromethoxy,difluoromethoxy, difluorochloromethoxy, trichloromethoxy,trifluoromethylthio, difluoromethylthio, difluorochloromethylthio ortrichloromethylthio; R²⁸ represents fluorine, chlorine, bromine, iodine,hydroxyl, cyano, C₁-C₄-alkyl, methoxy, ethoxy, methylthio, ethylthio,difluoromethylthio, trifluoromethylthio, C₁-C₂-haloalkyl orC₁-C₂-haloalkoxy having in each case 1 to 5 fluorine, chlorine and/orbromine atoms; R²⁹ represents hydrogen, fluorine, chlorine, bromine,iodine, cyano, C₁-C₄-alkyl, methoxy, ethoxy, methylthio, ethylthio,C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy having in each case 1 to 5 fluorine,chlorine and/or bromine atoms, C₁-C₂-alkylsulphinyl orC₁-C₂-alkylsulphonyl; R³⁰ represents methyl, ethyl or C₁-C₂-haloalkylhaving 1 to 5 fluorine, chlorine and/or bromine atoms; R³¹ representsmethyl or ethyl; Q¹ represents S (sulphur), SO or CH₂, p represents 0 or1, R³² represents methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5fluorine, chlorine and/or bromine atoms; R³³ represents methyl, ethyl orC₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine atoms;R³⁴ and R³⁵ independently of one another represent hydrogen, fluorine,chlorine, bromine, amino, methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5fluorine, chlorine and/or bromine atoms; R³⁶ represents hydrogen,fluorine, chlorine, bromine, iodine, methyl, ethyl or C₁-C₂-haloalkylhaving 1 to 5 fluorine, chlorine and/or bromine atoms; R³⁷ and R³⁸independently of one another represent hydrogen, fluorine, chlorine,bromine, amino, nitro, methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5fluorine, chlorine and/or bromine atoms; R³⁹ represents hydrogen,fluorine, chlorine, bromine, methyl, ethyl or C₁-C₂-haloalkyl having 1to 5 fluorine, chlorine and/or bromine atoms, R⁴⁰ represents hydrogen,fluorine, chlorine, bromine, amino, C₁-C₄-alkylamino,di(C₁-C₄-alkyl)amino, cyano, methyl, ethyl or C₁-C₂-haloalkyl having 1to 5 fluorine, chlorine and/or bromine atoms; R⁴¹ represents fluorine,chlorine, bromine, methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5fluorine, chlorine and/or bromine atoms; R⁴² represents hydrogen,fluorine, chlorine, bromine, amino, C₁-C₄-alkylamino,di(C₁-C₄-alkyl)amino, cyano, methyl, ethyl or C₁-C₂-haloalkyl having 1to 5 fluorine, chlorine and/or bromine atoms; R⁴³ represents fluorine,chlorine, bromine, methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5fluorine, chlorine and/or bromine atoms; R⁴⁴ represents fluorine,chlorine, bromine, methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5fluorine, chlorine and/or bromine atoms; R⁴⁵ represents hydrogen, methylor ethyl; R⁴⁶ represents fluorine, chlorine, bromine, methyl or ethyl;R⁴⁷ represents methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine,chlorine and/or bromine atoms; R⁴⁸ represents hydrogen, fluorine,chlorine, bromine, methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5fluorine, chlorine and/or bromine atoms; R⁴⁹ represents fluorine,chlorine, bromine, iodine, hydroxyl, C₁-C₄-alkyl, methoxy, ethoxy,methylthio, ethylthio, difluoromethylthio, trifluoromethylthio,C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy having in each case 1 to 5 fluorine,chlorine and/or bromine atoms; R⁵⁰ represents methyl, ethyl, n-propyl orisopropyl.
 3. A compound of formula (I) as defined in claim 1, where R¹is hydrogen or fluoro.
 4. A compound of formula (I) as defined in claim1, where R² is hydrogen or fluoro.
 5. A compound of formula (I) asdefined in claim 1, where R³ is C₂₋₆ alkyl, optionally substituted C₃₋₈cycloalkyl, phenyl, thienyl or furyl.
 6. A compound of formula (I) asdefined in claim 1, where R¹⁸ is difluoromethyl or dichloromethyl, R¹⁹is fluorine or chlorine, and R²⁰ is methyl.
 7. A compound of formula(II)

wherein R¹, R² and R³ is defined as in claim
 1. 8. A process forpreparing a compound of formula (I) as defined in claim 1, according tothe freaction scheme P0, wherein in step 1 a compound according toformula (III)

wherein R¹, R² and R³ is defined as in claim 1; are reacted in thepresence of a catalyst at elevated temperature and pressure to obtainthe compounds according to formula (II)

wherein R¹, R² and R³ is defined as in claim 1; wherein in step 2 thecompounds according to formula (II) as defined in step 1 are reactedwith compounds according to formula (IV)

with X being halogen or hydroxy; to obtain the compounds according toformula (I)

wherein A, R¹, R² and R³ is defined as in claim
 1. 9. A composition forcontrolling microorganisms and preventing attack and infestation ofplants therewith, wherein the active ingredient is a compound of formula(I) as claimed in claim 1, together with a suitable carrier.
 10. Amethod of controlling or preventing infestation of cultivated plants byphytopathogenic microorganisms by application of a compound of formula(I) as claimed in claim 1, to plants, to parts thereof or the locusthereof.